Modern Methods of Monosaccharide Synthesis from Non-Carbohydrate
Tomas Hudlicky,* David A. Entwistle, Kevin K. Pitzer, and Andrew J. Thorpe
Department of Chemistry, University of Florida, Gainesville, Florida 32611
Received December 18, 1995 (Revised Manuscript Received March 5, 1996)
2. Development of Sugar-Based Synthetic
3. Review of Enzymatic Manipulations Leading
4. Future Prospects of the Chemistry of Mono-
II. Synthesis of Monosaccharides
III. Synthesis of Cyclitols
IV. Synthesis of Azasugars
1. Hydroxylated Pyrrolidines
2. Hydroxylated Piperidines (alias Azasugars)
V. Synthesis of Amino Sugars
VI. Synthesis of Pseudosugars
Humans have utilized carbohydrates in natural
forms such as cellulose in cotton, sucrose in cane
sugar, and sucrose, D-fructose, and D-glucosein honey
from the dawn of civilization. However, the first
documented synthesis of a sugar-likesyrup presented
in the chemical literature was the preparation of
formose from formaldehyde reported in 1861 by
Boutlerow.1Formose was subsequently shown by
Fischer and Tafel to consist of a mixture of carbo-
hydrates, twoof which were identified as DL-arabino-
hexulose and DL-xylo-hexulose by preparation of the
phenylosazones 1 and 2, respectively (Figure 1).2
Osazone 1 was subsequently transformed to D-glu-
cose, D- and L-mannose, and also D- and L-fructose
by chemical and enzymatic (yeast fermentation)
The first documented enzymatic transformation of
one carbohydrate to another was the oxidation of
mannitol 3 to D-fructose 4 by means of Bacterium
aceticum by Brown in 1886 (Figure 2).3
This author also made a rather prophetic state-
ment that was to gain significance in the era of
biocatalysis, at a time some hundred years distant:
“...I think the experiments just described will be
of interest to biologists as well as chemists, as they
help to show that the vital functions of certain
organized ferments are most intimately connected
with the molecular constitution of bodies on which
The union of chemistry and biology witnessed in
the endeavors of the latter part of the twentieth
century accords this visionary statement complete
For almost one hundred years the chemistry of
sugars was dominated by structural and later ster-
eochemical investigations. With the advent of com-
plex synthetic ventures after World War II, sugars
were viewed as convenient sources of chirality for
asymmetric synthesis.4This discipline, made popu-
lar by Hanessian (see for example the synthesis of
C3-C17 segment of boromycin, Figure 3),5Fraser-
Reid,6and Fleet7,8among others, has stood as an
inspiration to chemists working in asymmetric syn-
thesis and in learning to manage asymmetry, its
transfer, and propagation.
F igure 1. Fischer and Tafel’s synthesis of nonracemic
sugars from formose.
F igure 2. The first enzymatic carbohydrate-to-carbohy-
F igure 3. Examples of targets synthesized from carbo-
Chem. Rev. 1996, 96, 1195−1220
0009-2665/96/0796-1195$25.00/0 © 1996 American Chemical Society
One of the disadvantages of sugars as chiral pool
reagents must surely bethenumber of protectiveand
deprotective manipulations required to manage the
fate of the asymmetric centers. As the regulatory
pressures on chemical manufacturing mounted in the
mid-1980s it became evident that synthetic ventures
of 20-30 steps in length would have diminished
practical or industrial credibility because of the
amount of waste mass which would accumulate
during such operations. Consequently new methods
of synthesis for carbohydrates began to emerge.
Synthesis of sugars from non-carbohydrate precur-
sors by means of clever chemical design and the use
of chiral auxiliaries such as those used by Vogel9
materialized in the 1980s. Parallel tothese develop-
ments was the assembly of simple sugars by the
exploitation of natural enzymatic pathways as ex-
emplified by the work of Wong.10,11Finally, a sys-
tematic design of carbohydrates and derivatives from
cis-cyclohexadienediols, derived from biological oxi-
dation of aromatics, pursued by Hudlicky, further
illustrated the power of biocatalysis in synthetic
chemistry.12The latter two methods, comprised of
the use of enzymes or whole cell fermentations, also
reflected the response to waste management and
Tomas Hudlicky was born in 1949 in Prague, Czechoslovakia, and,
following his arrival in the United States in 1968, he received his B.S. in
chemistry at Virginia Tech in 1973. He studied with Prof. E. Wenkert at
Rice University, where he received his Ph.D. in 1977. After a postdoctoral
fellowship with Prof. W. Oppolzer at the University of Geneva, he joined
the faculty at Illinois Institute of Technology in Chicago. In 1982 he moved
to Virginia Tech, where he was promoted to Professor of Chemistry in
1988, a position he held until moving to the University of Florida as
Professor of Chemistry in January 1995. Among the awards he has
received are the A. P. Sloan Fellowship (1981), the NIH Research Career
Development Award (1984), a Fulbright Fellowship at the University of
Montevideo, Uruguay, for a lectureship (1984−1985) and for research
(1985−1986), and the American Cyanamid Faculty Research Award
(1992). The research interests of the Hudlicky group include the
development of enantioselective synthetic methodologies, the design of
practical syntheses of natural products, enzymatic methods of synthesis,
and microbial degradation of aromatic hydrocarbons with prokaryotic
dioxygenases. The group has devoted considerable effort to the
implementation of general synthetic methodology for triquinane sesquit-
erpenes (1978−1988) and, more recently, for carbohydrates and deriva-
Dr. Kevin K. Pitzer was born on November 9, 1969, in New Castle, PA.
In 1991, he was commissioned a 2nd Lieutenant in the United States
Army and was graduated Magna Cum Laude from Gannon University
with a B.S. degree in Chemistry. In 1995, he earned a Ph.D. in Organic
Chemistry from Virginia Polytechnic Institute and State University under
the supervision of Dr. Hudlicky. Captain Pitzer is currently the Assistant
Chief, Organic Synthesis Division at the Walter Reed Army Institute of
Research. His current interests lie in the synthetic realm of medicinal
David Entwistle was born in 1969, in Chelmsford, England. He studied
chemistry at Imperial College of Science, Technology and Medicine, The
University of London, where he gained his B.Sc. (hons) in 1990.
Postgraduate research on the applications of dispiroketals in synthesis
under Professor Steven V. Ley F.R.S. at Imperial College of Science,
Technology and Medicine and The University of Cambridge resulted in
his Ph.D. from the former, in 1994. From 1994 to late 1995 he worked
with Professor Tomas Hudlicky at both Virginia Polytechnic Institute and
State University and The University of Florida on the synthesis of
pseudosugar monosaccharides and pseudosugar−inositol conjugates. He
is presently engaged as a postdoctoral teaching fellow at The University
of Nottingham under Professor Gerald Pattenden F.R.S. His research
interests include the development of new synthetic methods for the
synthesis of natural products.
Andrew Thorpe was born in Bolton, England, on December 3, 1968. He
received his B.Sc. in Medicinal Chemistry from University College London,
University of London, in 1990. He then joined Professor Stanley Robert’s
group at the University of Exeter where he studied synthetic approaches
to carbocyclic nucleosides and was awarded his Ph.D. in 1993. From
there he joined the Hudlicky research group developing novel routes to
disaccharide mimics. He is currently a postdoctoral research associate
with Eli Lilly and Company in Indianapolis.
Chemical Reviews, 1996, Vol. 96, No. 3Hudlicky et al.
regulation. Synthetic sequences were shorter, and
consequently their overall useful mass output greater.
See a recent survey of enzymatic methods in
It is clear that the synthetic chemist must join
forces with the biologist as the carbohydrate targets
desired by the pharmaceutical and medicinal com-
munity increase in complexity. It is unimaginable
that a chemical synthesis of a pentasaccharide con-
taining all unnatural sugars and utilizing natural
aldohexose sugars as starting materials would have
any value, given the astronomical number of steps
required to complete it.
This review intends to summarize those modern
methods of monosaccharide synthesis not directly
based on sugar-derived starting materials.
authors wish todirect the reader toan earlier review
of a similar type concentrating on sugar synthesis
from mainly acyclic precursors.)13A brief summary
and reference guide is provided for those methods
that do employ sugars as starting materials as
homage to the pioneering efforts of researchers in
their area. Excluded from this review are glycosi-
dation methods,14higher sugar synthesis,15and gly-
coprotein preparations.16The literature is covered
through December 1995.
2. Development of Sugar-Based Synthetic
None of the work presented in this review would
have been possible without the elegant work pub-
lished in 1891 by Emil Fischer.17As a tribute tohis
landmark achievement a synopsis of his work is
Aware of the basic topology of the carbohydrate
framework, Fischer performed a series of reactions
that elucidated the relative stereochemistry of D-
glucose, which continues to stand as an excellent
example of deductive reasoning. At the time the
absolute stereochemistry of glucose was unknown,
and Fischer arbitrarily assigned the configuration
shown.Later, X-ray crystallographic techniques
showed that his assignment was correct.
(a) The initial finding that D-glucose and D-man-
nose formed the same oxazone, 1, Figure 1, meant
that these compounds had the same C3, C4, and C5
stereochemistry. This implied that D-glucose and
D-mannose must be a pairing of either 5 and 6, 7 and
8, 9 and 10, or 11 and 12 (Figure 4).
(b) Both D-glucose and D-mannose were oxidized to
optically active diacids upon treatment with nitric
acid. This eliminated structures 5 and 11 as these
would givemesodiacids and, becauseof thenecessary
pairings, 6 and 12. This meant that D-glucose and
D-mannose were either 7 or 8 or 9 or 10 (Figure 4).
(c) Kiliani-Fischer chain extension of D-arabinose
gave D-glucose and D-mannose. This therefore re-
quires arabinose to have either the structure 13 or
14 (Figure 5).
(d) Arabinose was assigned the structure 13 be-
cause when it was oxidized with nitric acid it
produced an optically active diacid (structure 14
would havenecessarily given a mesodiacid 16). This,
when combined with (b), meant that D-glucose and
D-mannose were either 7 or 8.
(e) Finally it had to be decided whether structure
7 or 8 was that of glucose. Fischer devised a series
of reactions that exchanged the aldehyde and pri-
mary alcohol termini. When D-glucose was subjected
to that series, a new sugar was produced which
Fischer named L-gulose. When the termini of struc-
ture 7 are exchanged in this manner a new sugar 17
is formed, but when the termini of structure 8 are
exchanged structure 8 is regenerated (Figure 6).
This meant that the structure of D-glucose had tobe
as depicted in sugar 7.
Fischer’s publication. Initially structural elucidation
F igure 4. Part of the Fischer proof of glucose.
F igure 5. Fischer’s deduction of the relative stereochem-
istry of arabinose.
F igure 6. The final proof of the relative stereochemistry
Modern Methods of Monosaccharide SynthesisChemical Reviews, 1996, Vol. 96, No. 3
studies were explored, and then more involved chemi-
cal syntheses such as those of Lemieux were pur-
sued.18With the development of spectroscopic analy-
sis and the ease of identification, the synthesis of
other rare or unnatural sugars ensued. The recogni-
tion of the value of sugars as part of a “chiral pool”
also brought about the development of asymmetric
synthesis of non-carbohydrate natural products from
homochiral carbohydrate sources as well as the
concepts of “chiral templates” and “chirons” as ex-
tolled by Hannesian.4These syntheses related the
sugar stereochemistry to the target natural product
as can beseen in theexampleof the14-step synthesis
of quinic acid 20 from D-arabinose 13 (Scheme 1).19
The two key steps in the synthesis are the introduc-
tion of the endocyclic and exocyclic carbon atoms.
Even though these chiron approaches have great
merit, they in general requiremany steps, thelargest
proportion being protection-deprotection sequences.
The use of carbohydrates as a chiral pool resource in
organic synthesis continues; however, before com-
mitting to these lengthy sequences more notice
should be given to alternative synthetic methods.
A more recent example of the use of natural sugars
in the synthesis of carbocyclic natural products is the
“one-step” biocatalytic conversion of D-glucose 7 into
quinic acid 20 by means of genetically engineered
Escherichia coli (Scheme 2).20
One important role sugars have played in more
recent years is in the preparation of chiral auxilia-
ries.21Carbohydrate-derived chiral auxiliaries have
been used to introduce asymmetry into a host of
organic reactions. The chiral allyl titanate 21 has
been reacted with aldehydes yielding optically active
The simple allyl glucose
derivative 22 has successfully been used in asym-
metric Simmons-Smith cyclopropanations,23and
derivative 23 has been used as a dieneophile in
asymmetric Diels-Alder reactions (Figure 7).24
3. Review of Enzymatic Manipulations Leading to
With the heightened biological and medicinal in-
terest in carbohydrates in recent years, many new
methods for their construction have been developed.
Highly efficient and environmentally benign ways
haveinvolved theuseof enzymatic reactions in either
isolated or whole organism form.25-30
There are three main areas where enzymes have
been used in carbohydrate chemistry:30
(i) The synthesis of enantiomerically pure starting
materials for sugar synthesis. An example of this
strategy is the desymmetrization of glycerol deriva-
tives catalyzed by Pseudomonas sp. lipase (PSL)
Another example is the whole-cell use of the
dioxygenases present in the blocked mutants of
Pseudomonas putida, a soil bacterium that degrades
benzenes to substituted cyclohexadienediols 24
(Scheme 4). These dienediols have been shown tobe
versatilestarting materials in thesynthesis of a wide
variety of carbohydrates.
(ii) The direct formation of sugars by the use of
aldolases and also to a
ketolases.25-30The example below shows where 2-
deoxyribose-5-phosphate aldolase (DERA) has been
used toprepare unnatural 2-deoxyribose derivatives
25 (Scheme 5).32a,32b
(iii) Selectiveglycosidation reactions. Glycosidases
have been used for the synthesis of oligosaccharides
to a minor extent. Glycosyltranferases have had
more widespread use as exemplified in Scheme 6.33
aReagents: (i) Ni(R), H2; (ii) TrCl, Py. (iii) BnCl, KOH; (iv)
AcOH(aq); (v) TsCl, py; (vi) PPh3CH2; (vii) CH2O; (viii) Na, NH3;
(ix) Ac2O, py; (x) OsO4, NaIO4; (xi) HCN; (xii) HBr, AcOH; (xiii)
N2O3; (xiv) AcOH(aq).
F igure 7.
Chemical Reviews, 1996, Vol. 96, No. 3 Hudlicky et al.
natural and unnatural, by the combinations of the
best available techniques. With further advance-
ments of molecular modeling, bioactivemolecules will
be submitted to rational alterations and simpler or
more active surrogates will be developed. In this
regard there need not be the fear that organic
synthesis is not applicabletosuch problems. Already
it has been demonstrated that the best results in the
preparation of sugar derivatives are obtained by the
judicious combination of traditional and enzymatic
methods. Recent demonstration that halocyclohexa-
diene-cis-diols are chemically convertible to both
trans derivatives125allows the simple crossover be-
tween mannose and glucose diastereoselection, for
example, as shown in Scheme 67. Thus all of the
principles applied tothestereoselectivemanipulation
of cis-diols 24 demonstrated in the synthesis of most
derivatives of mannose-type monosaccharides can
now yield hexoses of the remaining biologically
important types. It is therefore appropriate to con-
clude this section with the demonstration that hith-
erto unknown classes of compounds, the inositol
conjugates shown in Scheme 68, can be prepared by
simple, iterative techniques from a simple precursor.
Once a combinatorial strategy of sugar synthesis
is reduced to practice, the iterative construction of
oligomers can beinitiated, again driven by thesimple
principles of functional differentiation and manage-
ment as illustrated in recent publications.126
The new class of inositol oligomers shown in
Scheme 68 contains compounds that are accessible
by simple procedures and with premeditated control
of regio-, stereo-, and enantiodisposition of function-
ality. Such compounds would not be easily made by
the application of either enzymatic or traditional
methods, and thus their synthesis demonstrates well
aReagents: (i) (Bromomethyl)chlorodimethylsilane, Et3N, DMAP, DCM; (ii)nBu3SnH, AIBN, PhH, reflux; (iii) KF, KHCO3, H2O2,
THF, MeOH, then Na2SO3; (iv) KHCO3, MeOH; (v) p-TSA, MeOH; (vi) Ac2O, py; (vii) DMP, PPTS, DMF; (viii) (COCl)2, DMSO, Et3N,
DCM, -78 °C; (ix) NaBH4, THF, MeOH.
aReagents: (i) MPMO(CdNH)CCl3, CSA, DCM; (ii) K2CO3, MeOH; (iii) Ph3P, p-NO2C6H4CO2H, DEAD, THF, then K2CO3, MeOH; (iv)
KH, ICH2SnBu3, THF; (v)nBuLi, THF, -78 °C; (vi) BH3-THF, -78 °C, then H2O2, NaOH; (vii) H2, Pd/C, MeOH; (viii) p-TSA, MeOH; (ix)
Ac2O, py; (x) TBS-Cl, imidazole, DMF; (xi) (COCl)2, DMSO, Et3N, DCM, -78 °C; (xii) NaBH4, MeOH; (xiii) NaH, THF, BnBr, Bu4NI; (xiv)
DDQ, DCM, H2O.
Modern Methods of Monosaccharide SynthesisChemical Reviews, 1996, Vol. 96, No. 3
the need for an open-minded union of chemical and
biological means of achieving preparative goals.
Where is the field of carbohydrate synthesis head-
ing? The question is impossible to answer, but one
may return totheprophetic pronouncement of Brown
quoted in the introduction of this review.
synthesis of natural and unnatural oligomers of
sugars, a marginally explored area today, holds a
great deal of potential in medicine and material
science, especially in the field of biodegradable poly-
mers. The combinatorial possibilities in carbohy-
drates are much greater than in peptides and there-
fore promise an almost infinite variability of new
Theauthors aregrateful toGenencor International
Inc., National Science Foundation, J effress Trust
Fund, TDC Research Inc., and TDC Research Foun-
dation for support of their research in carbohydrate
synthesis. Thetechnical assistanceand collaboration
of Dr. Gregg Whited (Genencor) and gifts of diol
metabolites arealsoappreciated. Thenames of many
co-workers who pursued the projects cited in this
review are given in appropriate citations.
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