Content uploaded by Usein M Dzhemilev
Author content
All content in this area was uploaded by Usein M Dzhemilev on Mar 26, 2025
Content may be subject to copyright.
Russian Chemical Reviews March 2025 94 (3)
ISSN 0036-021X
Volume 94 2025 Issue 3
Reviews on current topics in chemistry
ZIOC RAS
Uspekhi Khimii
Russian Chemical
Reviews
Zn
Cu
Zr
Ti
Fe
Co
Ni
Rh
Zn
- YIELDS
- REGIOSELECTIVITY
- STEREOSELECTIVITY
- COMPATIBILITY WITH FUNCTIONAL GROUPS
HIGH
RCR5158
© 2025 Uspekhi Khimii, ZIOC RAS, Russian Academy of Sciences
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
Russ. Chem. Rev., 2025, 94 (3) RCR5158
1. Introduction
Carbometallation reactions of acetylenes provide effective
methods for the regio- and stereoselective synthesis of
structurally diverse olefins. The most widely used transformations
of this type include Zr-catalyzed Negishi methylamination,1 – 3
cycloalumination,4 – 7 Dzhemilev cyclomagnesiation,8 – 13
carbocupration,14 carbostannylation,15 carboboration,16, 17 and
arylmagnesiation.18
The carbometallation of alkynes with organozinc reagents is
one of the most popular approaches to the synthesis of various
functionally substituted alkenes.19 – 28 The considerable interest in
the organozinc synthesis of these olefins is, first of all, due to the
tolerance of Zn reagents to the presence of heterofuctional
substituents in the substrates containing triple bonds.
This literature review is devoted to carbozincation reactions
of structurally diverse acetylene derivatives induced by transition
metal compounds. The mechanism of these reactions
considerably depends on the nature of the transition metal,
which is reflected in the structure of the review, which is divided
into parts, each addressing the catalytic transformations induced
by catalysts based on salts and complexes of a particular
Contents
1. Introduction 1
2. Catalysis by copper complexes 2
3. Catalysis and initiation of reactions 3
by zirconium and titanium complexes
4. Catalysis by iron complexes 6
5. Catalysis by cobalt complexes 7
6. Catalysis by nickel complexes 9
7. Catalysis by rhodium complexes 12
8. Conclusion 12
9. List of abbreviations and symbols 14
10. References 14
https://doi.org/10.59761/RCR5158
Catalytic carbozincation of acetylenic compounds
catalyzed by transition metal complexes
Ilfir R. Ramazanov,a* iD Rita N. Kadikova,a* iD Azat M. Gabdullin,a iD Usein M. Dzhemilev
b iD
a Institute of Petrochemistry and Catalysis, Ufa Federal Research Center of the Russian Academy
of Sciences, 450075 Ufa, Russia
b N.D.Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 119991 Moscow, Russia
Over the last 10 years, conceptually new results have been obtained in the field
of unsaturated organozinc reagents; these results need to be analyzed and
integrated. This review systematically considers data on the catalytic
carbozincation reactions of alkynes, which give alkenyl organozinc compounds,
highly reactive intermediates for the synthesis of functionally substituted
olefins. The reactions catalyzed by copper, iron, cobalt, nickel, and rhodium
complexes are described. A separate part of the review addresses the catalytic
reactions initiated by zirconium and titanium compounds. The reaction
conditions are indicated; in some cases, putative reaction mechanisms are
discussed.
The bibliography includes 135 references.
Keywords: alkynes, acetylenes, carbometallation, carbozincation, metal
complex catalysis.
I.R.Ramazanov. DSc in Chemistry, Professor of RAS, Head of the
Laboratory of Hydrocarbon Chemistry at the Institute of
Petrochemistry and Catalysis of the Ufa Federal Research Center of
the Russian Academy of Sciences.
E-mail: ilfir.ramazanov@gmail.com
Current research interests: aluminum carbenoids, carbometallation,
cyclopropanation, metallocomplex catalysis, organometallic
synthesis.
R.N.Kadikova. PhD in Chemistry, Senior Researcher at the same
laboratory.
E-mail: kadikritan@gmail.com
Current research interests: catalytic reactions, metallocomplex
catalysis, organoaluminum reagents, organozinc reagents, organo-
metallic chemistry, unsaturated compounds.
Received 19 November 2024
A.M.Gabdullin. PhD in Chemistry, Junior Researcher at the same
laboratory.
E-mail: saogabdullinsao@gmail.com
Current research interests: catalytic reactions, metallocomplex
catalysis, organoaluminum reagents, organozinc reagents, organo-
metallic chemistry, unsaturated compounds.
U.M.Dzhemilev. DSc in Chemistry, Corresponding Member of RAS,
Principal Researcher at N.D.Zelinsky Institute of Organic Chemistry
of the Russian Academy of Sciences.
E-mail: dzhemilev@mail.ru
Current research interests: carbo- and heterocyclic compounds,
chemistry of energy-rich molecules, chemistry of small molecules,
metallocomplex catalysis, organometallic chemistry, petrochemistry.
Translation: Z.P.Svitanko
Zn
Cu
Zr
Ti
Fe
Co Ni Rh
Zn
- YIELDS
- REGIOSELECTIVITY
- STEREOSELECTIVITY
- COMPATIBILITY WITH FUNCTIONAL GROUPS
HIGH
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
2 of 16 Russ. Chem. Rev., 2025, 94 (3) RCR5158
transition metal. It is noteworthy that carbozincation reactions
are considered in quite a few reviews (e.g., Refs 20 – 28), which
emphasizes high relevance of this subject for the development
of organic chemistry. However, in the last 10 years, conceptually
new results have been obtained in the field of unsaturated
organozinc reagents, and these results are to be summarized and
analyzed. First of all, this refers to recently developed methods
for carbozincation of acetylenic compounds catalyzed by the
Ti(OPri)4 – EtMgBr and Cp2ZrCl2 – EtMgBr systems (Cp is
cyclopentadienyl). The reactions of terminal acetylenes with
zinc catalyzed by iron(II) salts discovered at the same time also
appear unusual. One more finding is related to the use of Rh
catalysis, which allowed for decreasing the amount of the
catalyst to 3 mol.%. These achievements can have a substantial
impact on the subsequent trajectory of research in
carbometallation of not only alkynes but also other unsaturated
compounds. From this standpoint, the publication of this review
is timely and useful for the development of organometallic
chemistry.
By carbozincation of alkynes, we mean reactions in which
the carbon and zinc atoms add to a triple carbon – carbon bond.
A simple example is the reaction between an alkyne and an
organozinc compound. Diarylzinc derivatives are known to be
inert towards alkynes, while among dialkyl-containing
organozinc compounds, only di(tert-butyl)zinc can be mentioned
as being sufficiently nucleophilic to react with terminal
acetylenes in refluxing tetrahydrofuran.29 – 31 However,
disubstiuted acetylenes cannot be carbozincated by this reagent.
Allyl organozinc compounds have a higher reactivity, but in this
case, the carbozincation reaction has limitations. For example,
disubstituted acetylenes usually do not react. Meanwhile,
1-alkynylsilanes and 1-alkynyl sulfones with an activated triple
bond readily undergo regioselective carbozincation under the
action of allylzinc bromide in a THF solution.32 – 34 There are data
on successful carbozincation of N,N-diethylprop-2-yne-1-
amine,35, 36 but-3-yn-2-ol,37 – 41 propargyl alcohol,41, 42 and octa-
1,3-diyne
43 under the action of allyl organozinc compounds.
The reaction of phenyl- and butyl-substituted terminal acetylenes
with allylzinc bromide gives a mixture of mono- and bis-addition
products.
Thus, non-catalyzed carbozincation is characterized by the
following features:
(1) the use of a narrow range of organozinc compounds with
high nucleophilicity;
(2) the introduction of activated acetylenic substrates in the
reaction;
(3) more drastic conditions of the reaction (refluxing or long
reaction time) compared to those for analogous catalytic
reactions.
The use of transition metal catalysts based on transition metal
salts and complexes is the most versatile and convenient
approach to carbozincation of alkynes. The essence of catalytic
carbometallation of alkynes is that organic compound of
transition metal 1 is formed in situ and reacts with alkyne to give
substituted vinyl derivative of the transition metal 2 (Scheme 1).
The subsequent transmetallation of 2 with main group metal
(Zn, Al, Mg) compound 3 results in carbometallation product 4
and regeneration of catalytically active species 1. There are
various known approaches to initiation of the reaction, i.e., the
initial generation of intermediate 1. The key method is the
alkylation (arylation, alkenylation) of a transition metal salt with
an organic compound of a main group metal. The direction of
this reaction can be determined, at the qualitative level, from the
electronegativity values of the transition and main group metals.
The alkylation is expected to proceed towards the formation of
the salt with more ionic bond. The Pauling electronegativity of
zinc is 1.65, which is lower than the electronegativity of many
transition d elements. For this reason, salts of most transition
metals can theoretically catalyze carbozincation reactions.
However, the alkylation of lanthanide and actinide salts or salts
of d elements at the beginning of the period under the action of
organozinc compounds is problematic.
This review addresses carbozincation reactions of acetylenic
compounds catalyzed by copper, titanium, zirconium, iron,
cobalt, nickel, and rhodium salts and complexes. It is noteworthy
that all operations with organozinc compounds should be carried
out in an inert gas atmosphere using standard Schlenk techniques.
These reagents are exceptionally sensitive to the presence of
water and other protic solvents, and volatile dialkylzinc
derivatives can spontaneously ignite in air.
2. Catalysis by copper complexes
Organocopper compounds are reagents of choice for the
carbometallation of alkynes, as they provide high stereo- and
chemoselectivity of the reaction and are highly tolerant to the
presence of functional groups in the acetylenic substrate
molecule. Meanwhile, the carbometallation of functionally
substituted acetylenes such as 1-alkynyl sulfones on treatment
with organocopper reagents usually proceeds with low
stereoselectivity.44 – 49 This limitation of the carbocupration
reaction can be circumvented by using organozinc reagents.
Carbozincation of 1-alkynyl sulfones and sulfoxides catalyzed
by copper salts has been comprehensively studied. CuI-
Catalyzed carbozincation of the corresponding 1-alkynyl
sulfones with alkylzinc halides and dialkylzinc reagents has a
high regio- and stereoselectivity and gives exclusively (Z)-1-
alkenyl sulfones 5 and 6 in good to high yields (Scheme 2).
A similar carbocupration of alkynyl sulfones is non-selective,
giving a mixture of two stereoisomers.44 The Z- and E-isomer
ratio for these products considerably depends on temperature
and the nature of substituents at the triple bond and varies over a
broad range from 42 : 58 to 0 : 100. Alkenyl- and arylzinc
chlorides and bromides can be used as carbozincating reagents,
apart from alkyl derivatives.50, 51 A minor decrease in the yield of
the substituted alkenyl sulfone (down to 55%) takes place for
carbozincation of (hex-1-yn-1-ylsulfonyl)benzene with
carboxyl-containing reagent, MeOCO(CH2)3ZnI.28, 52
Cu-Catalyzed carbozincation of 1-alkynyl sulfoxides using
organozinc reagents, including functionally substituted ones, is
Scheme 1
LnMB–R1R2R3
R1
R2R3
MBLn
LmMA–R1
LnMB–X
R1
R2R3
MALm
LmMA–R1
LmMA–X
1
2
3
3
4
MA is main group metal (Zn, Al, Mg);
MB is transition metal (Cu, Zr, Ti, Fe, Co, Ni, Rh);
R1, R2, R3 is Alk, Ar or alkenyl
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
Russ. Chem. Rev., 2025, 94 (3) RCR5158 3 of 16
a stereoselective approach to the preparation of β,β-disubstituted
vinyl sulfoxides. Since the sulfinyl group can be easily replaced
by various functional groups, vinyl-substituted sulfoxides have
found wide use in organic synthesis.
1-Alkynyl sulfoxides containing alkyl, acyl, tributylsilyloxy,
or iodoalkyl group (Scheme 3)
53 were converted under the
indicated conditions to functionally substituted 1-alkenyl
sulfoxides 7, which formed as only Z-isomers in good yields. In
the case of 1-alkynyl sulfoxides with a bulky tert-butyl
substituent at the triple bond or a terminal triple bond, the yield
of β,β-disubstituted 1-alkenyl sulfoxides 7 decreased to
21 – 24%. To obtain products 8, copper(I) iodide, cyanide, or
trifluoromethanesulfonate (triflate, OTf) (2 mol.%) was allowed
to react with 2 equiv. of an organozinc compound containing
alkyl, allyl, benzyl, phenyl, pivaloyloxymethyl (PivOCH2),
carboxyl, or amine group in the molecule.53, 54
Mention should be made of the advantages of using
organozinc reagents over magnesium or lithium organic
compounds for carbometallation of alkynyl sulfoxides. For
example, the carbomagnesiation of 1-(hex-1-yn-1-ylsulfinyl)-4-
methylbenzene catalyzed by Cu(OTf)2 proceeds non-selectively
to give a mixture of two stereoisomers (E and Z) in 1 : 1.6
ratio.55, 56 In addition, at room temperature, α-sulfinyl vinyl
organozinc intermediates retain the stereoconfiguration at the
double bond, which is confirmed by the products of their
hydrolysis. Meanwhile, α-sulfinyl vinyl organolithium
intermediates undergo stereoisomerization even at –78°C,57, 58
which is attributable to higher ionicity of the C – Li bond and the
energetic advantage of the configuration inversion.
CuI-Catalyzed carbozincation of 1-alkynyl sulfoximines
results in the regio- and stereoselective formation of 1-alkenyl
sulfoximines 9 exclusively as the syn-addition products
(Scheme 4). This reaction was carried out for a broad range of
organozinc compounds that contained alkyl, phenyl, and
carboxyl groups.59 The yields of the resulting alkenyl sulfoximines
typically ranged from good to high. However, carbozincation on
treatment with oct-1-ynylzinc bromide afforded the
carbometallation product in a yield of only 18%.
Scheme 4
SR1
ON
Ar
Ts CuI (10 mol.%)
R2ZnY,
THF, 0°C, 3 h R2
ZnY
S
OR1
Ar
N Ts E–X
R2
E
S
OR1
Ar
NTs R1 = Me, Bun;
9 (18–92%)
R2 = Me, Et, Pri, Bun, Octn, Ph,
MeCO2(CH2)3, HexnC C,
Y = I, Br; E–X = HCl, I2, AllBr;
Ts is p-toluenesulfonyl,
Hex is hexyl, Oct is octyl
Et
Hexn;
The reaction of 1-alkynyl ketones with organozinc reagents
such as CF3CO2ZnR, where R = Et, Me, and Ph, in the presence
of 5 mol.% CuI and aromatic aldehyde in dichloromethane at
room temperature results in the regioselective formation of
methylenehydroxyl-substituted 1-alkenyl ketones 10, mainly as
Z-isomers, as shown in Scheme 5.60 Although authors of the study
call this reaction ‘CuI-catalyzed carbozincation of acetylenes’, it
is more appropriate to consider it as carbozincation of 1-alkynyl
ketones, because the transformation pathway proposed by the
authors implies addition of the metal to the oxygen atom of the
keto group in alkynyl ketone.61 Presumably, this reactions
proceeds via the step of formation of zinc-containing allenolate
anion. A similar transformation of alkynylones to allenolates
was reported by Noyori and co-workers
62 and by Japanese
chemists.63 – 65
Scheme 5
R1O
R2+R3CHO CF3CO2ZnR4
CuI, CH2Cl2, rt,
OOH
R2
R3
R4R1
15–20 h
10 (82–91%;
Z : E from 1.2 : 1 to 1 : 4)
R1 = Prn, Ph; R2 = Ph, Me;
R3 = Ph, p-Tol, 4-MeOC6H4;
R4 = Me, Et
3. Catalysis and initiation of reactions
by zirconium and titanium complexes
A number of publications
1, 66, 67 describe the carbozincation of
non-functionalized terminal and dialkyl-substituted acetylenes
with alkylzinc derivatives in combination with a stoichiometric
amount of zirconocene dihalides (Scheme 6). This zirconocene-
initiated reaction of alkynes with alkylzinc compounds (Et2Zn,
Me2Zn, Bun
2Zn, EtZnCl) was the first example of regio- and
stereoselective (the syn- to anti-addition product ratio exceeded
98 : 2) synthesis of 1-alkenylzinc derivatives 11.27, 67
Scheme 2
BunSO2Ph
BunSO2Ph
R ZnX
E–X BunSO2Ph
R E
5 (55–92%)
(a) RZnY, CuI (10 mol.%), THF, 0°C, 3 h;
R = Et, Pri, Bun, MeCO2(CH2)3;
Y = I, Br; E–X = HCl, I2, AllBr; E is electrophilic group, All is allyl
R1SO2Tol-p
ZnR2 (2 equiv.),
CuI (10 mol.%)
PhMe,
reflux, 5–12 min R2ZnR2
SO2Tol-pR1
NH4Cl (aq.)
R2H
SO2Tol-pR1
R1 = Ph, Bun;
R2 = Et, Me;
Tol is tolyl (methylphenyl)
6 (85–96%)
a
2
Scheme 3
FG(CH2)nS
p-Tol R2Zn (2 equiv.),
CuX (2 mol.%)
–78°C to rt R
SFG(CH2)n
p-Tol
O
7 (21–97%)
FG(CH2)n = Bun, TBSO(CH2)2, AcO(CH2)2, I(CH2)4, H, But ;
X = I, CN, OTf; R = Et, Me; FG is functional group, rt is room
temperature, TBS is tert-butyldimethylsilyl, Boc is tert-
butoxycarbonyl
O
BunS
p-Tol FG(CH2)nZnY,
CuX (2 mol.%)
FG(CH2)n
SBun
p-Tol
8 (72–87%)
FG(CH2)n = All, Bn, PivOCH2, EtO2C(CH2)3, BocNH(CH2)3;
X = Br, I; Y = I, CN, OTf
OO
–78°C to rt
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
4 of 16 Russ. Chem. Rev., 2025, 94 (3) RCR5158
The carbozincation of terminal and dialkyl-substituted
acetylenes with alkylzinc derivatives promoted by zirconocene
diiodide (Cp2ZrI2) takes place at room temperature, while the
use of Cp2ZrCl2 or Cp2ZrBr2 requires heating of the reaction
mixture at 50°C for 48 h. The reaction proceeds stereoselectively
as the syn-addition to the triple carbon–carbon bond. In the case
of terminal acetylenes, the reaction mainly gives the regioisomer
in which the zinc atom binds to the terminal carbon atom of the
alkyne. The Zr-promoted carbozincation of 5-iodopent-1-yne
with Et2Zn was utilized in a method for the synthesis of 1-ethyl-
2-iodocyclopent-1-ene 12.68 The allylzincation of dialkyl-
substituted acetylenes (dec-5-yne and but-2-yne) with diallyl- or
dicrotylzinc in the presence of a stoichiometric amount of
Cp2ZrI2 proceeds mainly as the syn-addition to give
carbometallation products in 84 – 92% yields.33 An exceptionally
high stereoselectivity was noted for the reaction involving
dicrotylzinc.
The reaction of dec-5-yne with Et2Zn can follow two
pathways depending on the procedure. When 2 equiv. of Et2Zn
and 1 equiv. of Cp2ZrI2 are used, the carbozincation followed by
iodinolysis proceeds stereoselectively (> 98%) to give (E)-5-
ethyl-6-iododec-5-ene 13 in 88% yield (Scheme 7).67 However,
analogous reaction of the same substrate with Et2Zn in the presence
of catalytic amounts of Cp2ZrCl2 and EtMgBr follows the 2-zinco-
ethylzincation pathway. The deuterolysis or iodinolysis give the
corresponding dideuterated or diiodinated trisubstituted olefins
14 (see Scheme 7).69 These pathways differ fundamentally by the
fact that in the latter case, the key intermediate is
zirconocene – ethylene complex 15, generated in situ upon the
reaction of zirconocene dichloride with Grignard reagent
(EtMgBr), rather than ethylzirconocene. The subsequent
coordination of the acetylenic compound and coupling of the
ethylene and acetylene moieties result in the generation of
zirconacyclopentene intermediate 16, which is transmetallated
with Et2Zn to give unsaturated organozinc compound 17.
Substituted propargylamines are successfully involved in the
2-zincоethylzincation reaction with Et2Zn catalyzed by the
Cp2ZrCl2 – EtMgBr system. After hydrolysis (deuterolysis or
iodinolysis), amino-substituted olefins 18 are obtained with high
regio- and stereoselectivity (the ratio of the syn- and anti-
addition products exceeds 95 : 5) (Scheme 8; the superscript ‘c’
stands for cyclo).70, 71 The presence of nitrogen atom in the
substrate does not induce destruction or deactivation of the catalytic
complexes.
Under similar conditions, 1-alkynylphosphines are converted
to phosphorus-containing organozinc compounds.72 It is known
that 1-alkenylphosphines are oxidized with air oxygen to
1-alkenylphosphine oxides.73 Therefore, the obtained 1-alkenyl-
phosphines were oxidized with an aqueous solution of H2O2 or
elemental sulfur to 1-alkenylphosphine oxides 19 and
1-alkenylphosphine sulfides 20.
Scheme 6
R1CCR2R2Zn (2 equiv.)
Cp2ZrX2 (1 equiv.),
20–22 or 50 °C,
3–48 h R3ZnY
R2
R1
R1 = Alk; R2 = H, Alk; R3 = Me, Et, Bun;
X = I, Br, Cl; Y = R3 or X
11 (70–95%;
E : Z = > 98% : 2)
I
1) BunLi,
hexane
2) EtZnCl,
CH2Cl2
I
ZnEt Et2Zn
Cp2ZrI2
Et ZnEt
ZnEt
I
1) evaporation
of CH2Cl2
2) addition
of THF
ZnEt
Et I2
I
Et
12 (58%)
3
Scheme 7
Bun
BunBunBun
Et I
13 (88%)
(a) 1) Et2Zn (2 equiv.), Cp2ZrCl2 (0.1 equiv.), EtMgBr (0.2 equiv.);
2) D2O or I2 (E = D or I);
(b) 1) Et2Zn (2 equiv.), Cp2ZrI2 (1 equiv.), rt; 2) I2
Bu
n
Bun
E
E
14 (73–76%)
Cp2ZrEt2
Cp2Zr
Cp2Zr
RR
Cp2ZrCl2
Cp2Zr
RR
2 Et2Zn
RR
EtZn
EtZn
15
16
17
EtZn
RR
or
EtMgBr –MgClBr
R = Bun
ab
Scheme 8
Et2Zn (2.5 equiv.),
Cp2ZrCl2 (0.1 equiv.),
EtMgBr (0.2 equiv.)
Et2O, rt, 18 h
D2O, or H2O,
or I2
1) H2O2) S8 (5.3 equiv.),
rt, 24 h
R
NR2
R
[Zn] [Zn]
NR2
R
EE
NR2
18 (60–90%)
Et2Zn (2.5 equiv.),
Cp2ZrCl2 (0.1 equiv.),
EtMgBr (0.2 equiv.)
Et2O, rt, 18 h
1) D2O
or H2O
R PPh2
R
PPh2
[Zn] [Zn]
R
PPh2
EE
19 (73–89%)
2) H2O2
O
Et R
PPh2
20
(79–81%) S
R = Bun, Prc;
NR2 = NMe2, piperidin-1-yl,
morpholin-4-yl;
E = D, H, I; [Zn] = ZnEt or Zn/2
R = Amn, Hexn, Octn; E = D or H; [Zn] = ZnEt or Zn/2;
Am is amyl
'
'
'
'
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
Russ. Chem. Rev., 2025, 94 (3) RCR5158 5 of 16
Thus, the formation of the key zirconocene–ethylene complex
15 in the reaction of substituted acetylenes with Et2Zn in the
presence of catalytic amounts of Cp2ZrCl2 and EtMgBr promotes
the formation of 2-zinco-ethylzincation products. Structurally
similar titanium – ethylene complex 21 is formed upon the
Kulinkovich reaction of Ti(OPri)4 with EtMgBr.74 For this
reason, it was obvious that the Ti(OPri)4 – EtMgBr system may be
active in the carbozincation reaction, like the Cp2ZrCl2 – EtMgBr
system noted above. Indeed, in 1998, Negishi and Montchamp
reported
75 the first intramolecular cyclization of enynes with
Et2Zn in the presence of catalytic amounts of Ti(OPri)4 and
EtMgBr, which selectively gave alkylidenecyclanes 22
(Scheme 9). Formally, this reaction can also be considered as
the carbozincation of the triple bond, because carbon and zinc
atoms finally add to the triple bond. According to the proposed
reaction mechanism,75 coupling of the multiple bonds of the enyne
molecule involving low-valent titanium – ethylene complex 21
leads to bicyclic titanacyclopentаdiene. The subsequent
transmetallation of this product on treatment with Et2Zn, with
the titanium atom being replaced by a zinc atom, yields
carbozincation product 23. It is noteworthy that the presence of
an oxygen atom in the enyne substrate molecule does not prevent
its intramolecular cyclization.
Scheme 9
Z
Y
Et2Zn (2.5 equiv.),
XTi(OPri)3 (0.1 equiv.),
EtMgBr (0.2 equiv.)
Et2O, hexane Y
Z
Zn/2
Zn/2
22 (53–99%)
H3O+ (I2 or D3O+),
Y
(E = H, D, I)
X = Cl, OPri;
Y = CH2, (CH2)2, O, CH2O;
Z = Ph, Me, Bun, SiMe3
Z
E
E
Z
Y
TiX4
Et2TiX2
2 EtMgBr
TiX2
YTiX2
Z
Et2TiX2
Et2Zn
Y
Z
Zn/2
Zn/2
21 23
H2O (D2O)
Y
Z
H(D)
H(D)
22
23°C, 3–48 h
On treatment with Et2Zn and catalytic amounts of Ti(OPri)4
and EtMgBr in dichloromethane at room temperature followed
by hydrolysis or deuterolysis, N-allyl-substituted propargyl-
amines are converted to (Z)-methylenepyrrolidines 24 in good
yields (Scheme 10).76 If iodinolysis of the reaction mixture
containing the organozinc intermediate is carried out instead of
the hydrolysis, diiodinated pyrrolidin-2-ones 25 are formed as a
result of oxidation involving the α-carbon atom of the pyrrolidine
ring. The Ti–Mg-catalyzed heterocyclization of N-benzyl-N-
(but-3-en-1-yl)hept-2-yn-1-amine with Et2Zn was used to obtain
(Z)-1-benzyl-4-methyl-3-pentylidenepiperidine.77
The Ti(OPri)4 – EtMgBr catalytic system is active towards
the carbozincation of 2-alkynylamines and 1-alkynylphosphines
on treatment with Et2Zn. As in the case of the Cp2ZrCl2 – EtMgBr
system, this reaction leads to regio- and stereoselective (the ratio
of the syn- and anti-addition products exceeds 95 : 5) formation
of nitrogen- and phosphorus-containing olefins 18 – 20.78, 79 The
reaction presumably involves the formation of low-valent
titanium – ethylene complex 21 by a mechanism similar to that
depicted in Scheme 9. However, in the case of 1-alkynyl-
phosphine sulfides, the conversion follows the ethylzincation
pathway and gives, after hydrolysis or deutrolysis, ethyl-
substituted olefin 26 (Scheme 11).79 The authors believe that the
presence of the sulfur atom at phosphorus facilitates the ligand
exchange between Et2Zn and titanacyclopentene, which is
formed upon the reaction of titanium – ethylene complex 21 with
the acetylene derivative. The subsequent intramolecular
disproportionation of alkenylethyl-titanium intermediate 27 is
accompanied by regeneration of the titanium – ethylene complex
and formation of ethylzincation product 28. The formation of a
similar bimetallic complex was postulated in the Zr-catalyzed
ethylmagnesiation reaction of non-activated olefins.80
Scheme 11
R P(S)Ph2
Et R
P(S)Ph2
R
Et E
P(S)Ph2
EtZn
(a) Et2Zn (2.5 equiv.), Ti(OPri)4 (0.15 equiv.), EtMgBr (0.2 equiv.),
Et2O, 18 h; (b) H2O or D2O; R = Alk; E = H or D
26 (69–82%)
Ti
(OPri)2
R
PPh2
(PriO)2Ti
ZnEt
H
(PriO)2Ti
Et
ZnEt
R
PPh2
R
Ph2PS
S ZnEt2Ti
(PriO)2
R
Ph2
P
Zn
S
Et
S
(PriO)2Ti
27
28
a b
Scheme 10
CH2Cl2, 18 h
Et2Zn (2.5 equiv.),
Ti(OPri)4 (0.15 equiv.),
EtMgBr (0.2 equiv.)
N
R2
R1
EE
N
R1
R2
N
R1
R2
[Zn] [Zn]
I2, H2O
R1 = 4-MeOC6H4, 4-ClC6H4, p-Tol, 2-furyl, 2-thienyl;
R2 = SiMe3, Ph, Bun, p-Tol, CH2NMe2
, piperidin-1-ylmethyl,
morpholin-4-ylmethyl, (CH2)4OMe; [Zn] = ZnEt or Zn/2;
24: E = H or D; 25: R1 = 4-MeOC
6
H
4,
p-Tol; R2 = SiMe
3
N
R1
R2
I
I
O
24 (69–91%)
25 (57–88%)
D2O
or H2O
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
6 of 16 Russ. Chem. Rev., 2025, 94 (3) RCR5158
4. Catalysis by iron complexes
The carbozincation of acetylenic compounds catalyzed by iron
salts or complexes has been little studied, being a new area of
metal complex catalysis. In 2021, regio- and stereoselective
vinylzincation of terminal alkynes was performed, with the ratio
of syn- and anti-addition products exceeding 95 : 5. As the
reagent, divinyl organozinc complex 29 was used in the presence
of iron-containing catalyst 30 stabilized by tridentate
1,10-phenanthrolinimine ligand; the reaction gave substituted
dienes 31 in a yield of up to 98% (Scheme 12).81
The developed method is characterized by high chemo-,
regio-, and stereoselectivity of the formation of carbozincation
products and high tolerance to the presence of N-, O-, S-, Si-,
and P-containing groups in the acetylenic substrate. When
FeCl2 is used as a catalyst in the absence of
1,10-phenanthrolinimine ligand, the reaction is non-selective
and, together with various carbozincation products, gives by-
products resulting from polymerization of acetylenic
compounds and product mixtures difficult to analyze. The
putative mechanism of the iron-catalyzed carbozincation
includes reduction of the initial iron(II) complex 30 to the
catalytically active vinylated iron(I) species 31. The
coordination of the terminal acetylene molecule to complex 31
gives, after the migratory insertion step, organoiron
intermediate 32. The subsequent transmetallation of this
intermediate with divinylzinc via σ-bond metathesis step
furnishes the alkyne carbozincation product, compound 33.
A similar strategy was implemented to perform regio-
and stereoselective (with a content of syn-addition product of
> 95%) Fe-catalyzed alkenylzincation of substituted acetylenes
with complex 34, incorporating dialkenylzinc, MgBr2, and LiCl
(Scheme 13).82 Catalyst 35 represented a complex of FeCl2 with
2,6-bis[1-(phenylimino)ethyl]pyridine. The proposed approach
is suitable for carbozincation of a broad range of terminal aryl-
substituted acetylenes, unsymmetrical diaryl- and dialkyl-
acetylenes and thus provides the synthesis of conjugated buta-
1,3-diene derivatives 36.
An unusual version of carbozincation of terminal acetylenes
was implemented with participation of alkyl iodides, bromides,
and tosylates in the presence of zinc and catalytic amounts of
FeBr2 and I2 (Scheme 14).83 – 86 The reaction affords
1,2-disubstituted olefins 37 with Z-configuration of the
Scheme 12
R + Zn · 2 MgBr2 · LiCl
2THF, rt, 1 h R
E
31 (up to 98%;
syn : anti = > 95 : 5)
R = Ar, Alk, alkenyl, CH2Ar, CH2CH2OBz, CH2CH2SO2Ph, CH2OTBDPS, CH2N(Boc)CH2Tol,
o-Tol, indol-1-yl, PPh2, SiPh3, C(O)N(Me)Ph, 2,6-dimethylphenylsulfanyl;
E = H, D, I; [Zn] = ZnCH=CH2; TBDPS is tert-butyldiphenylsilyl
R
[Zn] E+
29
30 (1–3 mol.%)
N
N
Fe
N
Me
Ar1
Ar2
Ph
migratory insertion
N
N
Fe
N
Me
Ar1
Ar2
Ph
N
N
Fe
N
Me
Ar1
Ar2Ph
σ-bond metathesis
(CH2=CH)2Zn
N
N
Fe
N
Me Ar1
Ar2Ph
Zn
N
N
Fe
N
Me
Ar1
Ar2
Ph (CH2=CH)2Zn N
N
Fe
N
Me
Ar1
Ar2
Cl
Cl
31 30
32
Ph
Zn
33
==
Scheme 13
THF, rt
R1R2
R1, R2 = Alk, Ar, Het; R3 = H, Alk;
Cat 35
(0.008–3 mol.%)
Zn · 2 MgBr2 · LiCl
2
R3
R1R2
XZn R3
R1R2
(D)H R3
36 (69–99%;
syn : anti = >95 : 5)
NFe
Ar
Ar
Cl
Cl
H2O (D2O)
34
35
+
Cat is catalyst
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
Russ. Chem. Rev., 2025, 94 (3) RCR5158 7 of 16
carbon – carbon bond. The role of iodine is to activate zinc; it
can be replaced by Me3SiI or CuBr2 (10 mol.%). This reaction
was successfully performed for aryl-substituted terminal
acetylenes containing various functional groups in the aryl
substituent, e.g., dimethylamine, trifluoromethyl, thiomethyl, or
thiophenyl group. The presence of a halogen atom (bromine,
chlorine, fluorine) in the aryl moiety of arylacetylene does not
prevent the reaction. However, when some functional group
such as carbonyl, amide, ester, aldehyde, or cyanide group is
present in the acetylenic substrate molecule, the yield of the
carbozincation product decreases to 32 – 58% and the
stereoselectivity is impaired.
Presumably, the reaction is initiated by reduction of FeBr2
with zinc to give FeBr (see Scheme 14).83, 87 The subsequent
reaction of FeBr with alkyl iodide gives the alkyl radical, which
reacts with terminal acetylene to give a substituted vinyl radical.
The reaction of the formed radical with FeBr is controlled by
steric factors and affords organoiron intermediate 38, which is
transmetallated under the action of ZnX2 to give carbozincation
product 39.
The developed strategy formed the basis for a new method of
the synthesis of (Z)-1-alkenylboronates 40 by carbozincation of
1-ethynylboronate with various secondary and tertiary alkyl
iodides and zinc in the presence of catalytic amounts of Fe(OTf)2
and Me3SiI (Scheme 15).88 The model reaction of tert-butyl
iodide with FeBr2 and I2 activator resulted in much poorer yields
and stereoselectivities: 48% yield and Z : E = 12 : 1 vs. 95% yield
and Z : E = 44 : 1 in the former case.
The carbometallation of ynamides is the most convenient and
versatile method for the synthesis of enamides and selective
synthesis of amino-functionalized olefins. Enamides are used in
organic synthesis as useful building blocks for the introduction
of nitrogen-containing functional groups into various aromatic
or non-aromatic heterocycles. The stereoselective methyl- and
ethylzincation of substituted ynamides was performed using
dimethyl- or diethylzinc in the presence of a stoichiometric
amount of FeCl2 (Scheme 16).89 The authors detected the
formation of only one stereoisomer. They assumed that the
reaction proceeds via generation of the ethyliron derivative
EtFeCl, which performs the carbometallation of ynamide. The
subsequent transmetallation of the formed iron-containing
intermediate 41 under the action of Et2Zn affords the
carbozincation product, which is hydrolyzed to give substituted
enamide 42. This mechanism is similar to that proposed for Cu-
catalyzed carbomagnesiation of acetylenic compounds.90
Scheme 16
R3
N
R1
R2
OR2Zn ( 2 equiv.),
FeCl2 (2 or 0.5 equiv.)
CH2Cl2, rt, 18 h
NR
3
R4
H
R1R2
O
R4 = Me, Et; R3 = Ph, Bun, CH2OBn, (CH2)2OMEM;
R1 = Ts, R2 = Bn;
ON
O,N
O
O
42 (13–91%)
FeCl2
Et2Zn
ClZnEt
EtFeCl N
OMEM
O
O
N
EtFe
Cl
O
OOMEM
Et2Zn
N
EtZn
Et
O
OOMEM
N
EtH
O
OOMEM
MEM = OOMe 41
42
H2O
R1C(O)NR2 =
4
5. Catalysis by cobalt complexes
The cobalt-catalyzed carbozincation of acetylenic compounds
was performed for the first time by Oshima and co-workers.91
The arylzincation by this procedure provides stereoselective
(> 99%) carbometallation of disubstituted acetylenes by the
ArZnI · LiCl complex in acetonitrile at 60°C to give the
corresponding arylzincation products 43 in 80 to 91% yields
(Scheme 17). The ArZnI · LiCl complex should be prepared in
advance as a THF solution using the procedure reported by
Krasovskiy et al.92
In the case of disubstituted acetylenes in which one substituent
is an aryl ring, the carbozincation is not only stereoselective, but
also regioselective, with products 43 and 44 being formed in
99 : 1 ratio. The zinc atom adds to the acetylene carbon atom
Scheme 14
2 FeIIX2 + Zn02 FeIX + ZnX2
FeIX + RI FeIIXI + R
RR'R'
RFeIXR'
R
FeIX
FeIX
XFeII
RR'
38
ZnX2
XZn
RR'
+R–I
(a) 1) FeBr2 (10 mol.%), Zn (1.5 equiv.), I2 (2 mol.%), DMA, rt,
16–24 h; 2) H2O;
R = Alk; FG = H, NMe2, OMe, SMe, But, Br, Cl, F, C(O)NEt2,
CO2Me, Ac, CHO, CN; DMA is dimethylacetamide
FG R
37 (32–79%;
Z : E from 7.4 : 1 to 50 : 1)
(1.0 equiv.) (1.5 equiv.)
FG
a
39
Scheme 15
HB
O
O+
40 (56–95%;
(a) Fe(OTf)2 (20 mol.%), Zn (3 equiv.), Me3SiI (2 mol.%),
DMA (0.5 M), 50°C;
R = But, Bus, 1-adamantyl, Amt, Hexc, Octs, Octc, 4-But-cyclohexyl
RB
O
O
Z : E from 7 : 1 to 44 : 1)
R–I a
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
8 of 16 Russ. Chem. Rev., 2025, 94 (3) RCR5158
bearing the aryl group. The carbozincation of unsymmetrical
dialkyl-substituted and terminal acetylenes gives ~1 : 1 mixtures
of regioisomers, which are formed in < 20% yields in the case of
terminal acetylenes. Moderate yields of the carbometallation
products (53 – 64%) are observed in the case of arylzincation of
dodec-6-yne on treatment with the 3-CF3C6H4ZnI · LiCl and
4-BrC6H4ZnI · LiCl complexes containing electron-withdrawing
substituents. The reaction is sensitive to steric factors and is
hampered when bulky 2-methylphenyl organozinc reagent is
used or if 2-methyldec-3-yne with the sterically hindered triple
bond serves as the substrate.
This method of carbozincation of acetylenic compounds in
the presence of cobalt(II) bromide catalyst has a number of
drawbacks. The implementation of this method requires
particularly aryl iodide, and the temperature of the synthesis of
organozinc compound must be strictly controlled. Furthermore,
different solvents are needed for different steps of the reaction,
namely, tetrahydrofuran is used for the synthesis of arylzinc,
while carbozincation of the acetylenic compound is performed
in acetonitrile.
The above drawbacks were eliminated in the procedure
proposed in two publications.93, 94 The procedure includes the
synthesis of arylzinc bromide by the reaction of aryl bromide
with zinc powder in the presence of allyl chloride and a catalytic
amount of the [CoBr2(bipy)] complex (bipy is 2,2'-bipyridine).
The filtration of the reaction mixture gives a solution of arylzinc
bromide 45 in acetonitrile, which is subsequently used for the
carbozincation of alkynes. This procedure was successfully
applied for the regio- and stereoselective synthesis (> 99% of the
corresponding isomers) of trisubstituted olefins 46 using
organozinc reagents containing either electron-donating or
electron-withdrawing substituents (Scheme 18). As a result,
alkenylaryl derivatives of ethers, esters, nitriles, chlorides,
fluorides, and sulfides were obtained. Complex 45 is suitable for
the arylzincation of acetylenic compounds with a sterically
hindered triple bond. Meanwhile, the above method of Co-
catalyzed carbozincation induced by ArZnI · LiCl (see
Scheme 17) proved to be inapplicable for the carbometallation
of sterically hindered alkynes.91
The arylzincation of disubstituted acetylenes with arylzinc
halide 47 in the presence of 5 mol.% [CoCl2(xantphos)] in
tetrahydrofuran at 60°C is accompanied by activation of the
ortho-C – H bond in the benzene ring of the carbometallation
product and formation of the organozinc compound 48
(Scheme 19).95, 96 The subsequent iodinolysis gives arylalkene
49 with a iodine atom in the aryl substituent. For stereoselective
transformation of arylalkylacetylenes into arylolefins 49 (isomer
ratio E : Z = > 50 : 1), 10 mol.% P(OPh)3 is used as a co-ligand.95
In the absence of the co-ligand, the ratio of E- to Z-isomer in the
reaction product ranges from 6 : 4 to 7 : 3. In the presence of
P(OPh)3 , the arylzincation of diphenylacetylene is also non-
selective (E : Z = 6 : 4). The Co-catalyzed arylzincation cannot
be performed for terminal acetylenes (phenylacetylenes, oct-1-
yne) and sterically hindered bis(trimethylsilyl)acetylene.
Scheme 19
ZnX
R R,
[CoCl2(xantphos)] (5 mol.%)
THF, 60°C, 4–12 h
ZnXH
RR
I2
IH
RR
[Co]
H[Co]
RR
[Co] H
RR
PhZnX
47
R = Alk, Ar, SiMe3; R' = OMe, NMe2, F, OBoc, CO2Et
R'R'
R'
R'R'
O
PPh2
PPh2
Xantphos 49 (44–95%)
48
R R,
Ynamides react with arylzinc bromides (e.g., p-anisylzinc
bromide) in the presence of 15 mol.% [CoBr2(phen)] (phen is
phenanthroline), formed in situ upon the reaction of CoBr2 with
phenanthroline in acetonitrile, to give enamides 50 and 51
(Scheme 20).97 High yields and high selectivities are inherent in
the carbozincation of 4-benzyl-3-(oct-1-yn-1-yl)oxazolidin-2-
one, which may be attributable to the presence of the bulky
benzyl substituent in the oxazolidine moiety of ynamide.
Meanwhile, the presence of the sterically hindered phenyl
substituent at the ynamide triple bond (see Scheme 20) prevents
the triple bond carbometallation and results in the formation of
amide 52 instead of enamide. This product is formed via the
hydration under the action of trifluoroacetic acid. The presence
of the trifluoroacetic acid in the reaction mixture is due to the
conditions of preparation of arylzinc bromide by the
[CoBr2(phen)]-catalyzed reaction of aryl bromide with zinc
powder in the presence of 15 mol.% trifluoroacetic acid.
The allylmetallation reactions make an important tool for the
synthesis of complex organic molecules with allyl groups.98, 99
Scheme 17
R R'
+
ArZnI · LiCl
(3 equiv.)
1) CoBr2 (5 mol.%),
MeCN, 60°C, 1.5–6 h
Ar H
R'R
+
HA
r
R'R
43 44
R = Alk, Ph, EtO2C(CH2)4;
R' = Alk, Ar, 2-thienyl, P(O)(OEt)2;
Ar = Ph, m-Tol, o-Tol, 4-BrC6H4, 4-EtO2CC6H4, 3-MeOC6H4,
3-F3CC6H4
Zn + LiCl + ArI
1,2-dibromoethane (5 mol.%),
Me3SiCl (1 mol.%)
THF, 50°C ArZnI · LiCl
(43 : 44 = >99 : 1
for R = Ar, R' = Alk)
2) H2O
(3 equiv.) (1.5 equiv.)
Scheme 18
Br
FG
[CoBr2(bipy)] (10 mol.%),
Zn (2 equiv.),
AllCl (30 mol.%)
MeCN, rt, 0.5–1.5 h
ZnBr
FG
45 (75–90%
after filtration)
R R'
H2O, rt, 0.5–24 h FG
R'
R
46 (56–76%)
R = Bun, Me, p-MeOC6H4CH2OCH2; R' = Bun, Pri, But,
p-MeOC6H4CH2OCH2; FG = 4-OMe, H, 4-CN, 4-CO2Et, 2-F, 4-Cl,
4-CF3, 4-Me, 4-SMe, 3,5-(CF3)2
(0.33 equiv.)
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
Russ. Chem. Rev., 2025, 94 (3) RCR5158 9 of 16
Allyl-substituted olefins 53 were obtained with high regio- and
stereoselectivity by the reaction of disubstituted alkynes with 4
equiv. of allylzinc bromide in THF in the presence of catalytic
amounts of CoCl2 (Scheme 21).100, 101 Electron-withdrawing
groups in the aryl substituent of the acetylenic substrate are
favourable for higher yields of diene 53. This reaction with
homopropargyl alcohols furnishes a mixture of two regioisomers
in low yields.
Scheme 21
R R'
CoCl2 (1.5–5 mol.%),
ZnBr
2) H2OH
R'R
53 (18–73%)
R = Alk; R' = Alk, Ar, (CH2)2OMe, CH2OH
(4 equiv.),
1)
THF, rt, 48 h
The benzylzincation of symmetrical acetylenes such as
oct-4-yne and 1,4-dibenzyloxybut-2-yne with BnZnBr
(3 equiv.) in the presence of catalytic amounts of CoBr2 and
(4-MeOC6H4)3P results in the formation of trisubstituted
olefins 54 in high yields (86 – 94%) and with high
stereoselectivities (> 99%) (Scheme 22).28, 102 High
regioselectivity [regioisomeric ratio (rr) of more than 99 : 1]
was also observed for the benzylzincation of terminal
acetylenes. However, the carbozincation of unsymmetrical
dialkyl-substituted acetylenes such as oct-2-yne gives 48 : 52
mixtures of regioisomers. The benzylzincation reaction is
sensitive to steric and electronic effects. For instance,
carbometallation of sterically hindered 2-methyldec-3-yne
with benzylzinc bromide and carbometallation of oct-4-yne
with electron-deficient 4-F3CC6H4CH2ZnBr barely take place.
The regio- and stereoselective CoI2(dppf)-catalyzed [dppf is
1,1'-bis(diphenylphosphino)ferrocene] carbozincation of
disubstituted acetylenes under the action of CO2 (1 atm) and
zinc metal (1.5 equiv.) in the presence of catalytic amounts of
Zn(OAc)2 and Et4NI (10 mol.%) can be exemplified by the
synthesis of carboxylate-substituted alkenyl organozinc
intermediates 55, which are converted to unsaturated carboxylic
acids 56 after deuterolysis (Scheme 23).103 Presumably, the
reaction starts with the generation of low-valent CoI(dppf) upon
the reaction of [CoI2(dppf)] with zinc.104 The subsequent
coupling of the acetylenic substrate with CO2 involving CoI
complex gives cobaltacycle 57, the transmetallation of which
via the reaction with ZnI2 and reduction by zinc lead to
carbozincation product 55.
Scheme 23
R'R
(a) CO2 (1 atm.), [CoI2(dppf)] (10 mol.%), Zn (dust) (1.5 equiv.),
Zn(OAc)2 (10 mol.%), Et4NI (10 mol.%), MeCN, DMF, 40°C;
R = Prn, Bun, SiMe3, Ph; R' = Prn, 2-thienyl, 1-naphthyl,
4-Me2NC6H4, 4-MeOC6H4, Ph
R'
R
Zn
COO D2O
R'
R
D
COOH
55 56 (52–82%)
R R'
CoII
, CO2
O
CoIII
R
R'
I
O
ZnI2
O
ZnI
O
R
R' CoIIII2Zn
O
Zn+
O
R
R'
+ ZnI2
55
57
a–
+
6. Catalysis by nickel complexes
Carbozincation of substituted acetylenes catalyzed by nickel
complexes is a convenient selective method for the preparation
of alkenyl organozinc compounds.105 The alkylzincation of
diphenylacetylene is conducted using 25 mol.% Ni(acac)2 (acac
is acetylacetone) in a mixture of THF with N-methyl-2-
pyrrolidone (NMP) in 3 : 1 ratio (v/v). The reaction is regio- and
stereoselective (98% content of one isomer for both types of
selectivity) at a temperature of –35°C within 3 – 18 h to give
1-alkenyl-substituted organozinc compound, which is hydro-
lyzed to yield substituted stilbenes 58 (Scheme 24).106, 107
Regarding alkylarylacetylenes, the most regioselective
(> 99% content of a single product) carbozincation is observed
for methyl- and ethyl-substituted acetylenes. The syn-addition
gives the regioisomer in which the zinc atom is attached to the
acetylenic carbon atom bearing the aryl group. This attests to the
crucial role of the electronic factor in the carbozincation of
acetylenic compounds.
As the alkyl chain length increases, the selectivity
of the reaction decreases. Indeed, the Ni(acac)2-catalyzed
ethylzincation of octylphenylacetylene is non-regioselective.
Scheme 20
ZnBr
OMe
+[CoBr2(phen)]
(74–80% total yield;
50 : 51 from 75 : 25 to 100 : 0)
1) filtration
RN
R'
EWG H
RN
OMe
R'
EWG
+H
RN
R'
EWG
MeO
R' = Bn, R = Hexn: EWG = Ts, CO2Bn, CO2Me;
O
N
O
O
N
O
Bn
N
O
Ts
Bn
Ph
PhN
Bn
Ts
,
52 (61%)
2) ynamide, MeCN,
–10°C, 1.5 h
; EWG is electron-withdrawing
group
50 51
R'–N–EWG =
Scheme 22
R'R
+
ArCH2ZnBr in THF
CoBr2 (5 mol.%),
(4-MeOC6H4)3P (10 mol.%)
EtCN, 25°C, 1.5–5 h ArCH2H
R'R
54 (40–94%;
E : Z from 92 : 8 to >99 : 1;
rr from 48 : 52 to >99 : 1)
R = Alk, BnOCH2, HO(CH2)2;
R' = Alk, H, CH2OBn;
Ar = p-Tol, o-Tol, m-Tol, 2-thienyl, 4-MeOC6H4, 4-ClC6H4,
4-BrC6H4, 4-F3CC6H4
(3 equiv.)
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
10 of 16 Russ. Chem. Rev., 2025, 94 (3) RCR5158
After the hydrolysis of the reaction mixture, a 7 : 1 mixture of
two regioisomeric trisubstituted olefins 59 and 60 (70% total
yield) and disubstituted alkene 61 (6% yield) are obtained (see
Scheme 24).106 The latter is formed upon the hydrolysis of the
product of octylphenylacetylene hydrometallation. Hetaryl-
acetylenes containing 2-thienyl, 5-pyrimidyl, and 2-pyridyl
substituents were also introduced in the Ni-catalyzed
ethylzincation reaction of disubstituted acetylenes on treatment
with Et2Zn.
The addition of phenyl group to alkynes was successfully
accomplished using Ni-catalyzed carbozincation with
diphenylzinc.106 – 108 In particular, a method for the synthesis of
(Z)-tamoxifen, an antiestrogen antitumour agent effective for
the treatment of metastatic breast cancer, was developed on the
basis of the reaction of 1-phenylbut-1-yne with diphenylzinc.105
Phenyl-substituted propargyl ethers add organozinc
compounds (Et2Zn, Pri2Zn, Ph2Zn) under mild conditions with
excellent stereoselectivity (Z : E = 98 : 2) to give, after hydrolysis,
(Z)-β-disubstituted allyl ethers.107 The ratio of the resulting
regioisomers is in the range from 90 : 10 to 100 : 0. The reaction
carried out at –35°C is usually completed within 1 h. The ethyl-
and methylzincation of (trimethylsilyl)phenylacetylene with
Et2Zn or Me2Zn gives the regioisomer in which the zinc atom is
attached to the acetylenic carbon atom bearing the trimethylsilyl
group (Scheme 25).107 It is noteworthy that the addition of
methylcuprates to substituted alkynes is more difficult, requiring
in some cases 120 h of the reaction.109, 110
Scheme 25
Et2Zn,
Ni(acac)2
(25 mol.%) Me3Si Ph
EtZn Et
THF–NMP (3 : 1),
–35°C
Me3Si Ph
I2Me3Si Ph
I Et
(31%)
According to the putative mechanism, Ni(асас)2-catalyzed
carbozincation of arylacetylenes starts with alkylation or
arylation of Ni(acac)2 with dialkyl- or diarylzinc to give nickel-
containing intermediate 62 (Scheme 26).106, 107 The subsequent
carbonickelation of arylacetylene with complex 62 results in the
formation of alkenyl organonickel intermediate 63. Compound
62 is transmetallated with RZn(acac), which results in
regeneration of the Ni(acac)2 catalyst and affords α-arylalkenyl
organozinc compound 64
The carbozincation reaction was used for the stereoselective
synthesis (97 – 100% content of a single isomer depending on
the brominating agent) of (Z)-(1-bromobut-1-ene-1,2-diyl)
dibenzene 65, the key intermediate for the preparation of a
selective estrogen receptor modulator.111 When a mixture of
Ph2Zn and Et2Zn is used in the reaction in the presence of
25 mol.% Ni(acac)2 (Scheme 27) to obtain (Z)-(1-iodobut-1-
ene-1,2-diyl)dibenzene 66, it is possible to decrease the amount
of Ph2Zn to 0.7 equiv. instead of 4 equiv. needed in the absence
of Et2Zn.107 The proportion of the ethylzincation product is
< 0.1% in this case. The authors attributed this result to the
formation of mixed organozinc reagent PhZnEt and to the higher
rate of transfer of the phenyl group to the nickel atom compared
to the ethyl group.
Scheme 27
EtPh 1) Ph2Zn (0.7 equiv.)
or Et2Zn (1.5 equiv.),
Ni(acac)2 (25 mol.%), 20°C
2) N
N
O
O
Br
Br
(1.5 equiv.)
Et Ph
BrPh
1) Ph2Zn (4 equiv.),
Ni(acac)2 (25 mol.%)
2) I2
Et Ph
IPh
66 (88%)
65 (65%)
THF–NMP (3 : 1), –35°C
A series of studies by Montgomery and Oblinger
112 – 114
demonstrated that Ni(cod)2 (cod is cycloocta-1,5-diene) initiates
the intramolecular carbozincation of alkynyl enone with
dialkylzinc or alkylzinc chloride (Scheme 28) giving rise to
alkylidenecyclopentane compound 67. The key intermediate is
the metallacyclopentane species formed as a result of coupling
of double and triple carbon–carbon bonds with participation of
nickel(0) π-complex.
Scheme 28
O
Ph
R1
Ni(cod)2 (0.04–0.06 equiv.),
Ph3P (0.2–0.3 equiv.),
R2Zn or R2ZnCl (2–3 equiv.)
THF, 0–25°C
OPh
R2
R1
R1 = H, Ph, Bun; R2 = Me, Bun, Ph, HC CH2
67 (38–82%)
2
The reaction is exceptionally sensitive to the nature of the
organozinc compound and to the presence of PPh3 . The reaction
of (E)-1-phenyloct-2-en-7-yn-1-one with Bun
2Zn in the absence
of PPh3 gives a mixture of compounds 68 and 69 (Scheme 29).115
In the presence of 25 mol.% PPh3, only 2-(2-methylienecyclo-
pentyl)-1-phenylethan-1-one 69 is formed. In the case of
Scheme 24
PhPh
R2Zn,
Ni(acac)2
(25 mol.%) Ph Ph
R ZnEt
THF–NMP
(3 : 1),
–35°C, 3–18 h
R = Et, Amn
H2OPh Ph
R H
58 (76–79%)
OctnPh
OctnPh
HEt
59 60 (9%) 61 (6%)
(69%, Z : E > 96 : 2)
+
OctnPh
EtH
OctnPh
HH
+
Et2Zn (2 equiv.),
THF, NMP, –35°C, 20 h
Ni(acac)2 (25 mol.%)
Scheme 26
R2Zn + R' Ar
Ni(acac)2
RNi(acac) R'Ar
R Ni(acac)
RZn(acac)
R'Ar
R ZnR
R'Ar
R2Zn
RZn(acac)
62
63
64
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
Russ. Chem. Rev., 2025, 94 (3) RCR5158 11 of 16
carbocyclization of alkynylenone under the action of Me2Zn
without PPh3 , the reaction is chemoselective, with target product
68 being formed in 82% yield.
The mechanism of alkynylenone cyclization proposed by the
authors (Scheme 30) is similar to the mechanism of enyne
cyclization induced with the Ti(OPri)4 – EtMgBr system. In the
case of pretreatment of Ni(cod)2 with triphenylphosphine,
intermediate 70 is transmetallated with ZnR3
2 to give bis-zinc
complex 71, which is hydrolyzed to give carbocycle 69. When
no PPh3 is present in the reaction mixture, intermediate 70
undergoes reductive elimination, resulting in regeneration of
LnNi0 and formation of carbocycle 72.
There is an example of intramolecular carbozincation
involving the aldehyde group and the triple carbon – carbon
bond in 5-ynals. This reaction is accompanied by the stereo-
selective formation of hydroxyl-substituted alkylidenecyclo-
pentanes 73 (Scheme 31).114 According to analysis of the product
by NMR spectroscopy, the reaction gives only one stereoisomer.
New synthetic potential of carbozincation is demonstrated by
combination of Ni-catalyzed acylzincation of alkylzinc halides
with ynamides induced by carbon(II) oxide (1 atm) and the
subsequent cross-coupling of in situ formed alkenylzinc halides
74 with aryl halides, which affords substituted enones 75
(Scheme 32).116 The Ni(acac)2 complex with the tridentate
4'-(p-tolyl)-2,2':6',2''-terpyridine (ttpy) ligand is used as the
catalyst.
Scheme 32
DMA,
25–50°C,
22 h
R N
R' ZnX (1.5 equiv.),
Ni(acac)2 (10 mol.%),
ttpy (20 mol.%),
CO (1 atm.)
RN
ZnX
74
X
O
R'O
X
O
EY,
RN
E
R'O
X
O
R = Ph, 4-FC6H4, 4-BrC6H4, o-Tol, PhCH=CH, H, BnOCH2,
Ph(CH2)2, Bun, TBSO(CH2)2; X = O, CH2;
R' = Bun, Me, Ph(CH2)2, EtO2C(CH2)3, AllCH2, Cl(CH2)6, Hexc,
cyclo-C5H9; E = H, I, Ph, 4-NCC6H4, 4-EtO2CC6H4; Y = Hal;
dba is dibenzylideneacetone
75 (36–73%)
N
N
N
Pd2(dba)3 (1.5 mol.%),
P(o-Tol)3 (10 mol.%)
ttpy
A series of studies
117 – 119 report coupling of a terminal
acetylene, 1-alkynylstannane, and α,β-unsaturated aldehyde in
the presence of trimethylchlorosilane induced by catalytically
active nickel, generated in situ by the reaction of Ni(acac)2 with
diisobutylaluminium hydride (DIBAL-H), which furnishes
enynal 76 (Scheme 33). The subsequent reaction of enynal 76 in
the presence of 0.1 equiv. of Ni(cod)2 with organozinc reagent,
generated in situ by the reaction of 2.5 equiv. of ZnCl2 with
organolithium or -magnesium compound, yields cyclohexenol
77.117 When substituted acroleins (crotonaldehyde and
methacrolein) are used, a mixture of diastereomers 77 in a ratio
from 1.2 : 1 to 5.3 : 1 is formed. However, the exocyclic double
bond formation in compound 77 is highly stereoselective in all
cases. The authors did not detect the formation of a reaction
product with a different stereoconfiguration of the double bond.
Scheme 29
R1
O
Ph
R2Zn
or R2ZnCl LnNi
R1
R2ZnO
Ph
H
H
without PPh
3
R2
R1
O
Ph
LnNi
R1
R2ZnO
Ph
H
H
R1
O
Ph
68
69
Without Ph3P: 68 (R1 = H:
R2 = Me, Bun, Ph) 51–82% yield;
69 (R1 = H, R2 = Bun) 11% yield;
with Ph3P (25 mol.%): 68 (R1 = H:
R2 = Me, Ph) 16–19% yield;
69 (R1 = H: R2 = Bun, Me, Ph) 47–92% yield
PPh3
2
Scheme 30
NiL
O
R2
R1
R2Zn R1
LnNi
R3
R2
R3ZnO
–LnNiR2
R1
Zn
R3
R2
R3ZnO
H3O+
R1
H
R2
O
69
LnNi0
R1
R3
R2
R3ZnO
H3O+
R1
R3
R2
O
68
70
71
72
R1
O
R2
Ni(cod)2
3
R2Zn
3
Scheme 31
R1
OHC
73 (62–76%)
Ni(cod)2
(5 mol.%)
THF, 0°C
ONi R1
Ln
ZnR2
R2
R1
HO R1 = H, Me, Ph;
R2 = Me, Et, Bun, Ph
2
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
12 of 16 Russ. Chem. Rev., 2025, 94 (3) RCR5158
7. Catalysis by rhodium complexes
In the rhodium-catalyzed carbozincation of disubstituted
acetylenes, an important factor is the ligand environment of
the central atom in the catalyst
120, 121 (Scheme 34). When the
ligand is cycloocta-1,5-diene, the carbozincation of non-
functionalized alkynes affords 2-arylalkenyl-organozinc
intermediates 78 via the formation of rhodium-containing
intermediate 79 (see Scheme 34). However, when
2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) is
used as the ligand, Rh-intermediate 79 undergoes
1,4-migration of the rhodium-containing substituent to give
intermediate 80, which is converted to ortho-alkenylaryl-
organozinc compound 81 upon ZnCl2-induced trans-
metallation.
A regio- and stereoselective synthesis of substituted
enamides 82 has been developed. The ratio of regioisomers
formed in the synthesis is >19 : 1.122, 123 The Rh(cod)(acac)-
catalyzed carbo zincation of ynamides containing
oxazolidinone, pyrrolidinone, or imidaziolidinone moiety
occurs on treatment with 2 equiv. of organozinc reagents in
THF (Scheme 35). As organozinc reagents, dialkyl and diaryl
zinc derivatives, including functionally substituted ones, were
used.
Scheme 35
XN
OR1
R2Zn or R2ZnY (2 equiv.),
Rh(cod)(acac) (5 mol.%)
THF, 0°C to rt, 15 min XN
O
82 (35–91%)
R1 = (CH2)2Ph, (CH2)2OTBS, Ph, Hexn;
X = O, NMe; R2Zn = Me2Zn, Et2Zn, Bu2Zn;
R2ZnY = ArZnI, ArCH2ZnBr, EtCO2(CH2)3ZnBr
R1
R2
2
2n
8. Conclusion
Three main types of mechanisms of catalytic carbozincation
(designated as I – III) can be distinguished (Scheme 36). The
first type is discussed in detail in the Introduction; the second
one is associated with the generation of low-valent transition
metal complexes and coupling reaction of the triple bond and
another unsaturated bond. As the unsaturated bond, double
carbon – carbon bond and aldehyde group were mentioned in the
review. The third type mechanism includes generation of an
alkyl radical, which reacts with terminal acetylene to give a
substituted vinyl radical. All three mechanisms afford the
carbometallation products. The review also presents reactions
that do not completely fit into this pattern, but include similar
carbometallation and transmetallation key steps.
The effect of substituents at the acetylenic carbon atoms on
the catalytic carbozincation reaction depending on the catalyst is
Scheme 33
H
O
R1
R2+R3
+
R4
SnBu3
(a) Ni(acac)2 (0.1 equiv.),
Me3SiCl (1.2 equiv.),
DIBAL-H (0.1 equiv.),
THF, 0°C to rt;
(b) R2Zn (2.5 equiv.),
Ni(cod)2 (0.1 equiv.),
THF, 0°C to rt, 0.25 h;
ONi R3
R2
R1
LL
R4
R3
R2
R1
ONi
O
LL
R4
R3
R2
R1
R4
R3
R2
R1
OH R5
77 (71–81%)
(1.2 equiv.) (1.1 equiv.)
(1 equiv.)
H2O
R1, R2 = H, Me; R3 = H; R4 = Ph; R5 = Et, Me; L = acac
76
n
a
5
bH2O
Scheme 34
ZnCl
X
+
R1R2
1) RhL (3 mol.%),
ZnCl2 (0.9 equiv.),
THF, 50°C, 1 or 5 h
2) E–X (1.8–3.0 equiv.) E
R2
R1
Xor
R2
R1
E
X
(for L = cod) (for L = BINAP)
X = Me, OMe, NMe2, SiMe3, CF3
;
R1, R2 = Alk, Ar, R3Si, CO2Me;
E–X = I2, D2O; L = cod or BINAP
(46 examples, 52–98%)
ZnCl
X
R1R2
ZnCl2[Rh]
X
transmetallation
[Rh]
R2
R1
X
ZnCl
R2
R1
X
[Rh]-Cl
arylrhodiation
ZnCl2
cod,
transmetallation
BINAP,
1,4-Rh migration
R2
R1
X
transmetallation
ZnCl2
R2
R1
X
78
80
[Rh]
ZnCl
79
81
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
Russ. Chem. Rev., 2025, 94 (3) RCR5158 13 of 16
illustrated in Table 1.† This Table analyzes the reactions that are
described in this review. Note that due to the great variety of
functionalized alkynes, all substituents in which the functional
group is separated from the acetylenic carbon atom by three or
more carbon atoms are indicated as alkyls. The columns that
give examples of carbozincation by mechanisms II and III are
marked by the words ‘cyclic’ and ‘radical’, respectively. The
cells containing the ‘plus’ sign correspond to cases for which the
corresponding reaction has been reported in the literature, i.e.,
the products formed as a result of carbozincation or further
functionalization have been isolated and characterized. The
empty cells correspond to combinations of reactants and
catalysts that have not been reported to react to afford the target
products. Actually, these are either unexplored reactions or
reactions that follow a different pathway and do not give
carbozincation products.
A similar Table was compiled to analyze the effect of
substituents in the organozinc compound on the catalytic
carbozincation reaction depending on the catalyst (Table 2). As
can be seen from these Tables, there are still quite a few
unexplored combinations of acetylenic substrates, organozinc
compounds, and transition metal-based catalysts. It is worth
noting that a systematic approach is applied to study the
carbozincation involving iron- and copper-containing catalysts.
In the former case, the influence of substituents at the triple bond
has been thoroughly investigated; in the latter case, organozinc
compounds of various natures have been used for the reaction.
Using Tables 1 and 2, it is possible to select an appropriate
combination of the reagents and the catalyst for a particular
substrate. All cases marked by the ‘plus’ sign in these Tables
mean that a synthetically available method has been developed.
It is obvious that study of certain combinations of reagents and
catalysts corresponding to empty cells in Tables 1 and 2 may
give rise to new catalytic approaches to the carbozincation of
alkynes.
However, in our opinion, a more interesting and non-
trivial task is to develop new methods for the carbozincation
of acetylenic compounds coupled with the activation of
aldehydes, ketones, nitriles, and small molecules (CO, CO2 ,
NO, SO2), This approach has good prospects for the synthesis
of valuable organic compounds, including pharmaceuticals.
This challenge is related to one more important question of
Scheme 36
RM MM
R
M M
MR R
M
IIII
II
Table 1. Effect of substituents at the carbon atoms of the triple bond on the catalytic carbozincation of functionally substituted acetylenes
(for any organozinc compounds).
Functional group Cu Zr/Ti Zr/Ti cyclic Fe Fe radical Co Ni Ni cyclic Rh
Alk + + + + + + + +
SiR3+ + + + +
B(OAlk)2+
Ar + + + + + + + +
Alkenyl +
CH2CH2OR + +
CH2NR2+ +
CH2OR + + +
C(O)NAlk2+
CO2Alk +
PPh2+ +
P(O)R2+ +
N(R)COR + + +
SO2Ar +
S(O)Ar +
Table 2. Effect of substituents at the zinc atom in the organozinc compound on the catalytic carbozincation of substituted acetylenes (for any
acetylenic substrates).
R-ZnX or R2Zn Cu Zr/Ti Zr/Ti cyclic Fe Fe radical Co Ni Ni cyclic Rh
Alk + + + + + + + +
Ar + + + + +
Vinyl, alkenyl + + + +
All + +
Bn + + +
Alkynyl + +
CH2OPiv +
† Here and in Table 2, the character R designates alkyl, aryl, benzoyl,
alkoxyl, and other groups.
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
14 of 16 Russ. Chem. Rev., 2025, 94 (3) RCR5158
why only particular transition metals were have been as
carbometallation catalysts.
An expansion of the range of catalytic systems would open
up new opportunities for the involvement of various substrates
into this reaction. Therefore, one more promising trend in the
studies of carbozincation is the search for new effective catalysts
for this reaction based on other transition metals. Furthermore,
rational design of catalytic systems could make it possible to
decrease the catalyst amount to < 1%. The carboalumination and
carbomagnesiation reactions alternative to carbozincation are
highly potent tools for the formation of new carbon–carbon
bonds. Using carbo- and cycloalumination reactions, effective
methods for the synthesis of practically important classes of
carbo- and metallacarbocycles, spirocarbocycles, and N-, O-, S-,
and P-containing heterocycles have been developed,73, 124 – 131
and new classes of biologically active terpenoid and steroid
compounds have been prepared.132 – 135 The carbomagnesiation
of alkynes, like carbozincation, is carried out using a broad
range of catalytic systems based on transition metals such as
copper, silver, titanium, zirconium, chromium, manganese, iron,
and nickel.28 In this series, it is necessary to mention magnesium, a
variety of organic derivatives of which are synthetically readily
available.
Despite all advantages of carboalumination and
carbomagnesiation reactions, the organozinc synthesis remains
a widely used tool in the armoury of organic chemistry. This is
caused by high tolerance of many functional groups to
organozinc reagents, which are synthetically available almost to
the same extent as organomagnesium compounds. Owing to the
large number of solvents used in the catalytic carbozincation,
ranging from dichloromethane to tetrahydrofuran, and to the
broad range of catalytic systems considered in this review, this
reaction is highly versatile. The subsequent development of
efficient catalysts for the carbozincation of unsaturated
compounds is of great interest as regards the design of efficient
and facile methods for obtaining practically important classes of
organic compounds.
The review was written within the State Assignment of the
Ministry of Science and Higher Education of the Russian
Federation (subjects FMRS-2025-0029 and FFZZ-2025-0008).
9. List of abbreviations and symbols
The following abbreviations and symbols are used in the review:
acac — acetylacetone,
All — allyl,
Am — amyl (pentyl),
BINAP — 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl,
bipy — 2,2'-bipyridine,
Boc — tert-butoxycarbonyl,
Cat — catalyst,
cod — cycloocta-1,5-diene,
Cp — cyclopentadienyl,
dba — dibenzylideneacetone,
DIBAL-H — diisobutylaluminium hydride,
DMA — dimethylacetamide,
dppf — 1,1'-bis(diphenylphosphino)ferrocene,
E — electrophilic group,
EWG — electron-withdrawing group,
FG — functional group,
Hex — n-hexyl,
MEM — 2-methoxyethoxymethyl,
NMP — N-methyl-2-pyrrolidone,
Oct — octyl,
PivOCH2 — pivaloyloxymethyl,
phen — phenanthroline,
rr — regioisomeric ratio,
rt — room temperature,
TBS — tert-butyldimethylsilyl,
TBDPS — tert-butyldiphenylsilyl,
TfO — trifluoromethanesulfonate (triflate),
Tol — tolyl (methylphenyl),
ttpy — 4'-(p-topyl)-2,2':6',2''-terpyridine,
Ts — p-toluenesulfonyl (tosyl),
xantphos — 9,9-dimethyl-4,5-bis(diphenylphosphino)-
xanthene.
10. References
1. D.E.Van Horn, E.Negishi. J. Am. Chem. Soc., 100, 2252
(1978); https://doi.org/10.1021/ja00475a058
2. E.Negishi. Pure Appl. Chem., 53, 2333 (1981);
https://dx.doi.org/10.1351/pac198153122333
3. E.Negishi, D.E.Van Horn, T.Yoshida. J. Am. Chem. Soc., 107,
6639 (1985); https://doi.org/10.1021/ja00309a036
4. U.M.Dzhemilev, A.G.Ibragimov, O.S.Vostrikova,
G.A.Tolstikov. Bull. Acad. Sci. USSR, Div. Сhem. Sci., 34, 196
(1985); https://doi.org/10.1007/BF01157356
5. U.M.Dzhemilev, A.G.Ibragimov. J. Organomet. Chem., 695,
1085 (2010); https://doi.org/10.1016/j.jorganchem.2010.01.002
6. V.A.D’yakonov, U.M.Dzhemilev. Reaction in Organic and
Organometallic Synthesis. (New-York: Nova Sci. Publ., 2010)
7. U.M.Dzhemilev, V.A.D’yakonov. In Modern
Organoaluminum Reagents. (Ser. Topic in Organometallic
Chemistry. Vol. 41). (Springer, 2012). P. 215;
https://doi.org/10.1007/3418_2012_38
8. U.M.Dzhemilev, A.G Ibragimov. Russ. Сhem. Bull., 47, 786
(1998); https://dx.doi.org/10.1007/BF02498144
9. U.M.Dzhemilev, A.G.Ibragimov, I.R.Ramazanov,
M.P.Lukyanov, A.Z.Sharipova. Russ. Сhem. Bull., 50, 484
(2001); https://dx.doi.org/10.1023/A:1011321526314
10. U.M.Dzhemilev, O.S.Vostrikova, R.M.Sultanov. Acad. Sci.
USSR, Div. Chem Sci., 32, 193 (1983);
https://dx.doi.org/10.1007/BF01167793
11. U.M.Dzhemilev, R.M.Sultanov, R.G.Gaimaldinov,
G.A.Tolstikov. Acad. Sci. USSR, Div. Chem Sci., 40, 1229
(1991); https://doi.org/10.1007/BF00961303
12. U.M.Dzhemilev, R.M.Sultanov, R.G.Gaimaldinov.
J. Organomet. Chem., 491, 1 (1995);
https://doi.org/10.1016/0022-328X(94)05198-K
13. U.M.Dzhemilev, O.S.Vostrikova. J. Organomet. Chem., 285,
43 (1985); https://doi.org/10.1016/0022-328X(85)87355-1
14. J.F.Normant, M.Bourgain. Tetrahedron Lett., 12, 2583 (1971);
https://doi.org/10.1016/S0040-4039(01)96925-4
15. E.Shirakawa, K.Yamasaki, H.Yoshida, T.Hiyama. J. Am.
Chem. Soc., 121, 10221 (1999);
https://doi.org/10.1021/ja992597s
16. M.Suginome, M.Shirakura, A.Yamamoto. J. Am. Chem. Soc.,
128, 14438 (2006); https://doi.org/10.1021/ja064970j
17. M.Daini, M.Suginome. Chem. Commun., 5224 (2008);
https://doi.org/10.1039/B809433K
18. E.Shirakawa, T.Yamagami, T.Kimura, S.Yamaguchi,
T.Hayashi. J. Am. Chem. Soc., 127, 17164 (2005);
https://doi.org/10.1021/ja0542136
19. A.G.Fallis, P.Forgione. Tetrahedron, 57, 5899 (2001);
https://doi.org/10.1016/S0040-4020(01)00422-7
20. Comprehensive Organic Synthesis. (2nd Edn). (Eds P.Knochel,
G.A.Molander). (Oxford: Elsevier, 2014)
21. Metal-Catalyzed Cross-Coupling Reactions. (2nd Edn).
(Eds A.de Meijere, F.Diederich). (Weinheim: Wiley-VCH,
2004)
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
Russ. Chem. Rev., 2025, 94 (3) RCR5158 15 of 16
22. G.Sklute, H.Cavender, I.Marek. In Organic Reactions. Vol. 87.
(Ed. S.E.Denmark). (Wiley, 2004). P. 507
23. J.F.Normant, A.Alexakis. Synthesis, 841 (1981);
https://doi.org/10.1055/s-1981-29622
24. I.Marek. J. Chem. Soc., Perkin Trans. 1, 535 (1999);
https://doi.org/10.1039/A807060A
25. J.V.N.V.Prasad, C.N.Pillai. J. Organomet. Chem., 259, 1
(1983); https://doi.org/10.1016/0022-328X(83)85153-5
26. W.Oppolzer. Angew. Chem., Int. Ed., 28, 38 (1989);
https://doi.org/10.1002/anie.198900381
27. The Chemistry of Organozinc Compounds. (Eds Z.Rappoport,
I.Marek). (Wiley, 2006)
28. K.Murakami, H.Yorimitsu. Beilstein J. Org. Chem., 9, 278
(2013); https://doi.org/10.3762/bjoc.9.34
29. L.Miginiac. J. Organomet. Chem., 238, 235 (1982);
https://doi.org/10.1016/S0022-328X(00)87033-3
30. G.Courtois, L.Miginiac. J. Organomet. Chem., 195, 13 (1980);
https://doi.org/10.1016/S0022-328X(00)93382-5
31. J.Auger, G.Courtois L.Miginiac. J. Organomet. Chem., 133,
285 (1977); https://doi.org/10.1016/S0022-328X(00)89127-5
32. G.A.Molander. J. Org. Chem., 48, 5409 (1983);
https://doi.org/10.1021/jo00174a066
33. E.Negishi, J.A.Miller. J. Am. Chem. Soc., 105, 6761 (1983);
https://doi.org/10.1021/ja00360a060
34. J.Li, S.You, M.Cai. J. Chem. Res., 8, 429 (2008);
https://doi.org/10.3184/030823408X3387
35. B.Mauzé, C.Nivert, L.Miginiac. J. Organomet. Chem., 44, 69
(1972); https://doi.org/10.1016/0022-328X(72)80043-3
36. C.Nivert, B.Mauz´e, L.Miginiac. C. R. Acad. Sci. Paris, Ser. C,
271, 271 (1970)
37. J.E.Baldwin, A.J.Rajeckas. Tetrahedron, 38, 3079 (1982);
https://doi.org/10.1016/0040-4020(82)80196-8
38. P.Knochel, C.Xia, M.C.P.Yeh. Tetrahedron Lett., 29, 6697
(1988); https://doi.org/10.1016/S0040-4039(00)82431-4
39. P.Knochel, J.F.Normant. Tetrahedron Lett., 27, 1039 (1986);
https://doi.org/10.1016/S0040-4039(86)80042-9
40. F.Bernadou, B.Mauze´, L.Miginiac. C. R. Acad. Sci. Paris,
Ser. C, 276, 1645 (1973)
41. T.Cuvigny, C.H.D.Penhoat, M.Julia. Tetrahedron, 43, 859
(1987); https://doi.org/10.1016/S0040-4020(01)90023-7
42. F.Bernadou, L.Miginiac. Tetrahedron Lett., 17, 3083 (1976);
https://doi.org/10.1016/0040-4039(76)80076-7
43. B.Mauzé. J. Organomet. Chem., 131, 321 (1977);
https://doi.org/10.1016/S0022-328X(00)84407-1
44. J.Meijer, P.Vermeer. Recl. Trav. Chim. Pays-Bas, 94, 14
(1975); https://doi.org/10.1002/recl.19750940107
45. V.Fiandanese, G.Marchese, F.Naso. Tetrahedron Lett., 19,
5131 (1978); https://doi.org/10.1016/S0040-4039(01)85830-5
46. J.J.Eisch, M.Behrooz, J.E.Galle. Tetrahedron Lett., 25, 4851
(1984); https://doi.org/10.1016/S0040-4039(01)91241-9
47. J.J.Eisch, M.Behrooz, S.K.Dua. J. Organomet. Chem., 285,
121 (1985); https://doi.org/10.1016/0022-328X(85)87362-9
48. M.Xie, X.Huang. Synlett, (4), 477 (2003);
https://doi.org/10.1055/s-2003-37524
49. M.Xie, J.Wang, X.Gu, Y.Sun, S.Wang. Org. Lett., 8, 431
(2006); https://doi.org/10.1021/ol052640i
50. M.Xie, X.Gu, J.Wang, J.Zhang, G.Lin, S.Wang.
Appl. Organomet. Chem., 23, 258 (2009);
https://doi.org/10.1002/aoc.1508
51. M.Xie, J.Wang, W.Zhang, S.Wang. J. Organomet. Chem., 694,
2258 (2009); https://doi.org/10.1002/aoc.1508
52. M.Xie, G.Lin, J.Zhang, M.Li, C.Feng. J. Organomet. Chem.,
695, 882 (2010);
https://doi.org/10.1016/j.jorganchem.2010.01.003
53. N.Maezaki, H.Sawamoto, R.Yoshigami, T.Suzuki, T.Tanaka.
Org. Lett., 5, 1345 (2003);
https://doi.org/10.1021/ol034289b
54. N.Maezaki, H.Sawamoto, T.Suzuki, R.Yoshigami, T.Tanaka.
J. Org. Chem., 69, 8393 (2004);
https://doi.org/10.1021/jo048747l
55. J.F.Poisson, J.F.Normant. J. Am. Chem. Soc., 123, 4639
(2001); https://doi.org/10.1021/ja015532+
56. J.F.Poisson, J.F.Normant. Org. Lett., 3, 1889 (2001);
https://doi.org/10.1021/ol015941a
57. G.H.Posner, P.W.Tang, J.P.Mallamo. Tetrahedron Lett., 19,
3995 (1978); https://doi.org/10.1016/S0040-4039(01)95121-4
58. O.Hisashi, M.Yoshiyuki, M.Morikazu, T.Hisashi. Chem. Lett.,
7, 517 (1978); https://doi.org/10.1246/cl.1978.517
59. G.Sklute, C.Bolm, I.Marek. Org. Lett., 9, 1259 (2007);
https://doi.org/10.1021/ol070070b
60. A.B.Flynn, W.W.Ogilvie. Chem. Rev., 107, 4698 (2007);
https://doi.org/10.1021/cr050051k
61. S.Xue, L.He, Y.K.Liu, K.Z.Han, Q.X.Guo. Synthesis, 666
(2006); https://doi.org/10.1055/s-2006-926299
62. M.Kitamura, T.Miki, K.Nakano, R.Noyori. Bull. Chem. Soc.
Jpn., 73, 999 (2000); https://doi.org/10.1246/bcsj.73.999
63. M.Taniguchi, T.Hino, Y.Kishi. Tetrahedron Lett., 27, 4767
(1986); https://doi.org/10.1016/S0040-4039(00)85060-1
64. M.Taniguchi, S.Kobayashi, M.Nakagawa, T.Hino, Y.Kishi.
Tetrahedron Lett., 27, 4763 (1986);
https://doi.org/10.1016/S0040-4039(00)85059-5
65. S.Kinoshita, H.Kinoshita, T.Iwamura, S.I.Watanabe,
T.Kataoka. Chem. – Eur. J., 9, 1496 (2003);
https://doi.org/10.1002/chem.200390169
66. К.Maruoka, Y.Fukutani, H.Yamamoto. J. Org. Chem., 50,
4412 (1985); https://doi.org/10.1021/jo00222a051
67. E.Negishi, D.E.Van Horn, T.Yoshida, C.L.Rand.
Organometallics, 2, 563 (1983);
https://doi.org/10.1021/om00076a021
68. E.Negishi, H.Sawada, J.M.Tour, Y.Wei. J. Org. Chem., 53,
913 (1988); https://doi.org/10.1021/jo00239a054
69. E.I.Negishi, T.Takahashi. Sci. Synth., 2, 681 (2003);
https://doi.org/10.1055/sos-SD-002-00797
70. R.N.Kadikova, I.R.Ramazanov, A.M.Gabdullin,
O.S.Mozgovoj, U.M.Dzhemilev. RSC Adv., 11, 4631 (2021);
https://doi.org/10.1039/D0RA10132J
71. A.M.Gabdullin, R.N.Kadikova, I.R.Ramazanov. Russ. J. Org.
Chem., 59, 2132 (2023;
https://doi.org/10.1134/S1070428023120102
72. A.M.Gabdullin, R.N.Kadikova, O.S.Mozgovoj,
I.R.Ramazanov. Russ. Chem. Bull., 73, 1900 (2024);
https://doi.org/10.1007/s11172-024-4307-6
73. I.R.Ramazanov, R.N.Kadikova, Z.R.Saitova, U.M.Dzhemilev.
Asian J. Org. Chem., 4, 1301 (2015);
https://doi.org/10.1002/ajoc.201500274
74. D.M.Fischer, H.Lindner, W.M.Amberg, E.M.Carreira. J. Am.
Chem. Soc., 145, 774 (2023);
https://doi.org/10.1021/jacs.2c11680
75. E.Negishi, J.-L.Montchamp. J. Am. Chem. Soc., 120, 5345
(1998); https://doi.org/10.1021/ja973841n
76. R.N.Kadikova, I.R.Ramazanov, A.M.Gabdullin,
O.S.Mozgovoj, U.M.Dzhemilev. RSC Adv., 10, 17881 (2020);
https://doi.org/10.1039/D0RA02677H
77. A.M.Gabdullin, R.N.Kadikova, I.R.Ramazanov. Russ. J. Org.
Chem., 60, 1600 (2024);
https://doi.org/10.1134/s1070428024080049
78. R.N.Kadikova, I.R.Ramazanov, A.M.Gabdullin,
O.S.Mozgovoj, U.M.Dzhemilev. Synlett, 30, 311 (2019);
https://doi.org/10.1055/s-0037-1612009
79. R.N.Kadikova, I.R.Ramazanov, A.M.Gabdullin,
O.S.Mozgovoj, U.M.Dzhemilev. Catalysts, 9, 1022 (2019);
https://doi.org/10.3390/catal9121022
80. D.P.Lewi, R.J.Whitby, R.V.H.Jones. Tetrahedron, 51, 4541
(1995); https://doi.org/10.1016/0040-4020(94)01139-Q
81. Q.Huang, Y.X.Su, W.Sun, M.Y.Hu, W.N.Wang, S.F.Zhu.
J. Am. Chem. Soc., 144, 515 (2021);
https://doi.org/10.1021/jacs.1c11072
82. W.Wang, Q.Huang, Y.Jin, Y.Q.Zhou, S.Zhu. Chin. J. Chem.,
41, 547 (2023); https://doi.org/10.1002/cjoc.202300356
83. C.W.Cheung, F.E.Zhurkin, X.Hu. J. Am. Chem. Soc., 137,
4932 (2015); https://doi.org/10.1021/jacs.5b01784
I.R.Ramazanov, R.N.Kadikova, A.M.Gabdullin, U.M.Dzhemilev
16 of 16 Russ. Chem. Rev., 2025, 94 (3) RCR5158
84. F.E.Zhurkin, X.Hu. J. Org. Chem., 81, 5795 (2016);
https://doi.org/10.1021/acs.joc.6b01306
85. C.Wang, C.Wu, S.Ge. ACS Catal., 11, 7585 (2016);
https://doi.org/10.1021/acscatal.6b02654
86. C.W.Cheung, X.Hu. Chem. – Eur. J., 21, 18439 (2015);
https://doi.org/10.1002/chem.201504049
87. A.Darù, X.Hu, J.N.Harvey. ACS Omega, 5, 1586 (2020);
https://doi.org/10.1021/acsomega.9b03578
88. G.Barzanò, A.Cheseaux, X.Hu. Org. Lett., 21, 490 (2019);
https://doi.org/10.1021/acs.orglett.8b03772
89. H.Lingua, F.Vibert, D.Mouysset, D.Siria, M.P.Bertrand,
L.Feray. Tetrahedron, 73, 3415 (2017);
https://doi.org/10.1016/j.tet.2017.04.065
90. G.Evano, B.Michelet, C.Zhang. C. R. Chimie, 20, 648 (2017);
https://doi.org/10.1016/j.crci.2016.12.002
91. K.Murakami, H.Yorimitsu, K.Oshima. Org. Lett., 11, 2373
(2009); https://doi.org/10.1021/ol900883j
92. A.Krasovskiy, V.Malakhov, A.Gavryushin, P.Knochel. Angew.
Chem., Int. Ed., 45, 6040 (2006);
https://doi.org/10.1002/anie.200601450
93. M.Corpeta, C.Gosmini. Chem. Commun., 48, 11561 (2012);
https://doi.org/10.1039/C2CC36676B
94. P.Knochel, A.K.Steib. Synfacts, 9, 0203 (2013);
https://doi.org/10.1055/s-0032-1318069
95. B.H.Tan, J.Dong, N.Yoshikai. Angew. Chem., Int. Ed., 51,
9610 (2012); https://doi.org/10.1002/ange.201204388
96. A.D.Dilman, V.V.Levin. Tetrahedron Lett., 57, 3986 (2016);
https://doi.org/10.1016/j.tetlet.2016.07.080
97. R.Sallio, M.Corpet, L.Habert, M.Durandetti, C.Gosmini,
I.Gillaizeau. J. Org. Chem., 82, 1254 (2017);
https://doi.org/10.1021/acs.joc.6b02612
98. E.Negishi, D.Y.Kondakov. Chem. Rev., 96, 417 (1996);
https://doi.org/10.1039/CS9962500417
99. Y.Yamamoto, N.Asao. Chem. Rev., 93, 2207 (1993);
https://doi.org/10.1021/cr00022a010
100. Y.Hiroto, N.Toshihiro, Y.Hideki, O.Koichiro. Bull. Chem. Soc.
Jpn., 79, 1271 (2006); https://doi.org/10.1246/bcsj.79.1271
101. T.Nishikawa, H.Yorimitsu, K.Oshima. Synlett, (9), 1573
(2004); https://doi.org/10.1055/s-2004-829086
102. K.Murakami, H.Yorimitsu, K.Oshima. Chem. – Eur. J., 16,
7688 (2010); https://doi.org/10.1055/s-0030-1257959
103. K.Nogi, T.Fujihara, J.Terao, Y.Tsuji. J. Am. Chem. Soc., 138,
5547 (2016); https://doi.org/10.1021/jacs.6b02961
104. K.Hiroyoshi, I.Keiji. Bull. Chem. Soc. Jpn., 54, 1015 (1981);
https://doi.org/10.1246/bcsj.54.1015
105. Transition Metals for Organic Synthesis. Vol. 1.
(Eds M.Beller, C.Bolm). (Weinheim: Wiley, 2004)
106. T.Stüdemann, P.Knochel. Angew. Chem., Int. Ed. Engl., 36, 93
(1997); https://doi.org/10.1002/anie.199700931
107. T.Stüdemann, M.Ibrahim-Ouali, P.Knochel. Tetrahedron, 54,
1299 (1998); https://doi.org/10.1016/S0040-4020(97)10226-5
108. P.Knochel. In Transition Metals for Organic Synthesis.
(Eds M.Beller, C.Bolm). (Weinheim: Wiley-VCH, 1998).
P. 467
109. R.S.Iyer, P.Helquist. Org. Synth., 64, 1 (2003);
https://doi.org/10.1002/0471264180.os064.01
110. A.Marfat, P.R.McGuirk, P.Helquist. J. Org. Chem., 44, 1345
(1979); https://doi.org/10.1021/jo01322a034
111. R.O.Cann, R.E.Waltermire, J.Chung, M.Oberholzer,
J.Kasparec, Y.K.Ye, R.Wethman. Org. Process Res. Dev., 14,
1147 (2010); https://doi.org/10.1021/op100112r
112. J.Montgomery, E.Oblinger, A.V.Savchenko. J. Am. Chem.
Soc., 119, 4911 (1997); https://doi.org/10.1021/ja9702125
113. J.Montgomery. Acc. Chem. Res., 33, 467 (2000);
https://doi.org/10.1021/ar990095d
114. E.Oblinger, J.Montgomery. J. Am. Chem. Soc., 119, 9065
(1997); https://doi.org/10.1021/ja9719182
115. J.Montgomery, A.V.Savchenko. J. Am. Chem. Soc., 118, 2099
(1996); https://doi.org/10.1021/ja952026+
116. Y.Zhang, Q.Cao, Y.Xi, X.Wu, J.Qu, Y.Chen. J. Am. Chem.
Soc., 146, 7971 (2024); https://doi.org/10.1021/jacs.4c02023
117. M.Lozanov, J.Montgomery. J. Am. Chem. Soc., 124, 2106
(2002); https://doi.org/10.1021/ja0175845
118. S.Ikeda, Y.Sato. J. Am. Chem. Soc., 116, 5975 (1994);
https://doi.org/10.1021/ja00092a061
119. S.Ikeda, K.Kondo, Y.Sato. J. Org. Chem., 61, 8248 (1996);
https://doi.org/10.1021/jo961236h
120. J.Ming, T.Hayashi. Org. Lett., 20, 6188 (2018);
https://doi.org/10.1021/acs.orglett.8b02668
121. J.Ming. PhD Thesis. Nanyang Technological University,
Singapore, 2018
122. B.Gourdet, H.W.Lam. J. Am. Chem. Soc., 131, 3802 (2009);
https://doi.org/10.1021/ja900946h
123. B.Gourdet, M.E.Rudkin, C.A.Watts, H.W.Lam. J. Org. Chem.,
74, 7849 (2009); https://doi.org/10.1021/jo901658v
124. I.R.Ramazanov, R.N.Kadikova, A.K.Amirova, O.S.Mozgovoj,
U.M.Dzhemilev. RSC Adv., 11, 39518 (2021);
https://doi.org/10.1039/D1RA08268J
125. I.R.Ramazanov, R.N.Kadikova, A.K.Amirova,
U.M.Dzhemilev. Dokl. Chem., 494, 155 (2020);
https://doi.org/10.1134/S0012500820100031
126. R.N.Kadikova, I.R.Ramazanov, A.K.Amirova, O.S.Mozgovoj,
U.M.Dzhemilev. Russ. Chem. Bull., 71, 2149 (2022);
https://doi.org/10.1007/s11172-022-3640-x
127. I.R.Ramazanov, R.N.Kadikova, A.K.Amirova, O.S.Mozgovoj.
Mendeleev Commun., 33, 693 (2023);
https://doi.org/10.1016/j.mencom.2023.09.032
128. V.A.D’yakonov, O.A.Trapeznikova, A.Meijere,
U.M.Dzhemilev. Chem. Rev., 114, 5775 (2014);
https://doi.org/10.1021/cr400291c
129. V.A.D’yakonov, A.L.Makhamatkhanova, R.A.Agliullina,
L.K.Dilmukhametova, T.V.Tyumkina, U.M.Dzhemilev.
Beilstein J. Org. Chem., 12, 406 (2016);
https://doi.org/10.3762/bjoc.12.43
130. F.Guillen, J.-C.Fiaud. Tetrahedron Lett., 40, 2939 (1999);
https://doi.org/10.1016/S0040-4039(99)00329-9
131. T.V.Tyumkina, R.R.Nurislamova, A.L.Makhamatkhanova,
L.M.Khalilov, U.M.Dzhemilev. Organometallics, 37, 2406
(2018); https://doi.org/10.1021/acs.organomet.8b00200
132. L.U.Dzhemileva, R.A.Tuktarova, U.M.Dzhemilev,
V.A.D’yakonov. Cancers, 15, 756 (2023);
https://doi.org/10.3390/cancers15030756
133. V.A.D’yakonov, R.A.Tuktarova, L.U.Dzhemileva,
S.R.Ishmukhametova, M.M.Yunusbaeva, U.M.Dzhemilev.
Steroids, 138, 14 (2018);
https://doi.org/10.1016/j.steroids.2018.06.002
134. V.A.D’yakonov, R.A.Tuktarova, L.U.Dzhemileva,
S.R.Ishmukhametova, M.M.Yunusbaeva, U.M.Dzhemilev.
Steroids, 138, 6 (2018);
https://doi.org/10.1016/j.steroids.2018.06.004
135. U.M.Dzhemilev, V.A.D’yakonov, R.A.Tuktarova,
T.A.Gloriozova, L.U.Dzhemileva, A.O.Terent’ev,
V.M.Dembitsky. Vietnam J. Chem., 56, 661 (2018);
https://doi.org/10.1002/vjch.201800066
