Kari Rissanen

University of Jyväskylä | JYU · Department of Chemistry

Halogen-bonded complexes are utilized across a myriad of synthetic chemistry fields, with halogen(I) complexes such as Barluenga’s reagent ubiquitous with respect to halogenation reactions. Especially the preparation of Barluenga’s reagent requieres the use of heavy metal salts and vast amounts of chlorinated solvents. In line with a more modern, e...

In recent years, the studies of RNA and its use for the development of RNA based vaccines have increased drastically. Although cyanine dyes are commonly used probes for studying nucleic acids, in a wide range of applications, there is still a growing need for better and brighter dyes. To meet this demand, we have systematically studied the structur...

The first tris (O‒I‒N) carbonyl hypoiodites have been synthesised based on trimesic acid and pyridine or 4-methylpyridine, with their structures definitively confirmed by single crystal X-ray diffraction (SCXRD). The more soluble...

In recent years, 3-aminopiperidine and 3-aminoazepane have been identified as important pharmacophores that led to the development of drugs having several billion dollar global revenues. Although the number of protocols for the resolution of suitable racemic derivatives is steadily increasing, there is an ongoing demand for new synthetic methods to...

New chiral tetranuclear square-like homo- and heterometallamacrocycles containing allyl-palladium and either {Pd(P-P)*} or {Pt(P-P)*} optically pure moieties (P-P* = (2S,3S)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphanyl)butane ((S,S)-DIOP) and (2S,4S)-2,4-bis(diphenylphosphanyl)pentane ((S,S)-BDPP)) have been obtained by the self-assemb...

Halogen bonding occurs between a positive region of a polarized halogen (X), most commonly with an iodine or bromine atom. The polarization, caused by an electron withdrawing group (R), induces electron deficiency onto the halogen atom, creating an electropositive region known as a σ-hole. This σ-hole then interacts with electron-rich nucleophiles...

An easily accessible colorimetric probe, a carbazole–naphthaldehyde conjugate (CNP), was successfully prepared for the selective and sensitive recognition of Sn(II) in different commercially‑available toothpaste and mouth wash samples. The binding mechanism of CNP for Sn2+ was confirmed by UV–Vis, 1H, and 13C NMR titrations. The proposed sensing me...

The development of purely organic fluorescence emitters is of great importance for their low cost and high performance. Responding to this demand, carbazole is a promising emitter due to its extensive freedom for functionalisation, high thermal and chemical stability, as well as low cost. Herein, the effect of protonation on the fluorescence of var...

N-Alkyl ammonium resorcinarene chloride receptors, NARX4, have been shown to act as high-sensitivity detectors of pyrophosphate (PPi), a biomarker of disease, in aqueous media through the chloride-to-PPi exchange [NAR(Cl)4 to...

The Cover Feature shows the cascade sequence for the synthesis of a wide variety of novel N‐fused indolines under mild conditions from simple indoles. Iron and hydrochloric acid mediate the reduction of the nitro‐group and dearomatizing cyclization of indoles. In this study, the dearomatizing cyclization also proceeds well with Cu(OTf)2 or TfOH as...

Learning to stabilize palladium dimers Catalyst optimization is often difficult to do rationally. Once something works, it may be unclear which specific features underpin the performance. A case in point is the stabilization of palladium(I) dimers, which has relied on a very small class of phosphine ligands. Hueffel et al . used machine learning to...

Six bile acid alkyl amide derivatives were studied with respect to their gelation properties. The derivatives were composed of three different bile acids with hexyl or cyclohexyl side chains. The gelation behaviour of all six compounds were studied for 36 solvents with varying polarities. Gelation was observed mainly in aromatic solvents, which is...

New 1-2 nm macrocyclic iodine(I) complexes prepared via a simple ligand exchange reaction, manifest rigid 0.5-1 nm cavities that bind hexafluorophosphate anion in the gas phase. The size of the cavities and the electrostatic interactions with the iodine(I) cations influence the anion binding properties of these macrocyclic complexes.

TBS-protected or NH-sulfonimidamides react with β-alkoxyvinyl trifluoromethylketones under solvent-free mechanochemical conditions to give 3-trifluoromethyl-substituted three-dimensional 1,2,6-thiadiazine 1-oxides. C4-Functionalized products can be obtained by starting from cyclic enones and brominations of the initially formed heterocycles. The st...

Four b is (O‒I‒N) compounds have been synthesised from various dihypoiodites and 4-ethylpyridine. The compounds were characterised in both the solution and solid states by NMR spectroscopy ( ¹ H, ¹⁵ N), X-ray diffraction, and...

The synthesis of iodine(I) complexes with either benzoimidazole or carbazole-derived sp2 N-containing Lewis bases is described, as well as their corresponding silver(I) complexes. The addition of elemental iodine to the linear two-coordinate Ag(I) complexes produces iodine(I) complexes with a three-center four-electron (3c-4e) [N-I-N]+ bond. The 1H...

Subsequent reduction and dearomatizing cyclization reactions open up an entry into the synthesis of novel N‐fused polycyclic indolines. The dearomatizing cyclization as key step of the sequence proceeds well with Cu(OTf)2 or TfOH as catalyst. At elevated temperature reduction of nitro‐substituted precursors with iron under acidic conditions affords...

Environmental pollution with chiral organic compounds is an emerging problem requiring innovative sensing methods. Amino-functionalized thioureas, such as 2-(dimethylamino)cyclo-hexyl-(3,5-bis(trifluoromethyl)phenyl)thiourea (Takemoto's catalyst), are widely used organocata-lysts with virtually unknown environmental safety data. Ecotoxicity studies...

A mechanochemical van Leusen pyrrole synthesis with a base leads to 3,4-disubstitued pyrroles in moderate to excellent yields. The developed protocol is compatible with a range of electron-withdrawing groups and can also be applied to the synthesis of oxazoles. Attempts to mechanochemically convert the resulting pyrroles into porphyrins proved to b...

Trapping of volatile unbranched C6hydrocarbons (hexane, 1-hexene, and 1-hexyne) in a 1D coordination polymer is reported. The guest inclusion was studied quantitatively by¹H-NMR analysis and thermogravimetric measurements, while synchrotron single-crystal diffraction data allowed advancing the view of their confinement into linear CP channels. Adso...

In recent years the excessive use of hydazine containing chemical pesticides and insecticides in farming practices are well pronounced, that directly or indirectly impart a great threat towards the total...

A series of neutral halogen-bonded O–I–N complexes were prepared from in-situ formed carbonyl hypoiodites and aromatic organic bases (pyridine, DMAP, 4-morpholinopyridine and 4-piperidinopyridine). The carbonyl hypoiodites exhibit a very strongly polarized iodine atom with larger sigma-holes than any known uncharged halogen bond donor. The hypoiodi...

A series of neutral halogen-bonded O–I–N complexes were prepared from in-situ formed carbonyl hypoiodites and aromatic organic bases (pyridine, DMAP, 4-morpholinopyridine and 4-piperidinopyridine). The carbonyl hypoiodites exhibit a very strongly polarized iodine atom with larger sigma-holes than any known uncharged halogen bond donor. The hypoiodi...

A self-assembled metallobox from copper(II) and two macrocycles containing 1H-pyrazole ligands has been prepared. The internal cavity of the box is able to selectively encapsulate a single chloride anion over...

A series of compressed M[Li3(1)3Ti2] (M = Li, Na, K, Rb, Cs) and expanded helicates M4[(1)3Ti2] has been obtained. The helicates Li3[M(1)3Ti2] or M4[(1)3Ti2] with M = Na+, K+, Rb+, or Cs+ adopt the expanded structure in solution. Upon crystallization cation-translocation based isomerism leads to the compressed structures M[Li3(1)3Ti2] (M = Na, Rb).

We report a remote functionalization strategy, which allows the Z-selective synthesis of silyl enol ethers of (hetero)aromatic and aliphatic ketones via Ni-catalyzed chain walking from a distant olefin site. The positional selectivity is controlled by the directionality of the chain walk and is independent of thermodynamic preferences of the result...

Iodonium complexes have been synthesised incorporating tertiary amines to study and explore why such species comprised of alkyl amines are relatively rare. Complexes were characterised in solution (1H and 15N NMR spectroscopy), the solid state (SCXRD), and analysed computationally.

The synthesis of di- and tritopic gold(i) metallaligands of the type [(Au4-py)2(μ2-diphosphane)] (diphosphane = bis(diphenylphosphanyl)isopropane or dppip (1), 1,2-bis(diphenylphosphanyl)ethane or dppe (2), 1,3-bis(diphenylphosphanyl)propane or dppp (3) and 1,4-bis(diphenylphosphanyl)butane or dppb (4)) and [(Au4-py)3(μ3-triphosphane)] (triphosphan...

The generality of nucleophilic iodonium interactions (NIIs) has been demonstrated by preparing a range of silver(I) and iodonium (I+) complexes and studying their 15N NMR chemical shifts, with the first example of a NII-complex involving a 2-coordinate silver(I) complex being confirmed by X-ray crystallography, and its nucleophilicity studied by DF...

Upon application of a multicomponent Petasis reaction, a broad range of NH-sulfoximines and boronic acids react with glyoxalic acid to afford the corresponding 2-substituted acetic acids with N-bound sulfoximidoyl groups. The protocol features excellent yields under ambient, metal-free conditions and short reaction times. Furthermore, the applicabi...

Herein, a copper(II)‐catalyzed dearomative cyclization amination of N‐(2‐aminobenzoyl) indoles is presented. Under mild reaction conditions, the cyclization proceeds to afford tetracyclic indolines by forming a new C−N bond in good yields. The tetracyclic 5a,6‐dihydroindolo[2,1‐b]quinazolin‐12(5H)‐ones are obtained in good to excellent yields (up t...

Based on the DFT‐level calculated molecular volume (V mol ) of pyrrole and its liquid density, pyrrole manifests the highest liquid density coefficient LD c (defined as [V mol • density • 0.6023]/FW) value of 0.7. Normal liquids have LD c < 0.63. This very high LD c is due to the strong N‐H … π interactions in solution and hence pyrrole can be cons...

The work herein describes the synthesis of five three-coordinate silver(I) complexes comprising a bidentate ligand L1, either bpy (2,2′-bipyridyl) or bpyMe2 (4,4′-dimethyl-2,2′-dipyridyl), and a monodentate ligand L2, either mtz (1-methyl-1H-1,2,3-triazole), 4-Etpy (4-ethylpyridine), or 4-DMAP (N,N-dimethylpyridin-4-amine). Upon reaction of the thr...

Biginelli-type multicomponent reactions (MCRs) with NH-free sulfonimidamides provide 2,3-dihydro-1,2,6-thiadiazine 1-oxides in high yields. The couplings are performed in a planetary ball mill under solvent-free mechanochemical conditions. Acetic acid or ytterbium triflate are used as catalysts. A representative product was characterized by X-ray s...

Unlike the closely related and widely investigated amidino-substituted benzimidazoles and benzothiazoles with a range of demonstrated biological activities, the matching benzoxazole analogues still remain a largely understudied and not systematically evaluated class of compounds. To address this challenge, we utilized the Pinner reaction to convert...

By visible‐light photoredox catalysis with copper complexes, sulfoximidoyl chlorides add to terminal aryl alkynes to give the corresponding ( E )‐ β ‐chlorovinyl sulfoximines with exclusive regio‐ and stereoselectivities in high yields. Two representative products have been characterized by X‐ray crystal structure analysis. Radicals appear to be de...

Hexamethylenetetramine (HMTA) and N-haloimides form two kinds of short (CO)2N–X···N and Y–X···N (X, Y = Br, I) halogen bonds. Nucleophilic substitution or ′′ligand-exchange′′ reaction on the peripheral Y of Y–X···N with chloride of N-chlorosuccinimide leads to Cl–X···N halogen-bonded complexes. The X···N distances are significantly shorter when X i...

The synthesis of four novel gold(i)-phosphane complexes coordinated to 9-phenanthrene chromophore has been carried out through the reaction of 9-phenanthreneboronic acid and the corresponding AuClPR3 (PR3 = PPh3 for triphenylphosphane (1a); 1,4-bis(diphenylphosphanyl)butane or dppb (2b); bis(diphenylphosphanyl)acetylene or dppa (2c); (AuCl)2(diphos...

The complexation of (3aR,7aR)-N-(3,5-bis(trifluoromethyl)phenyl)octahydro-2H-benzo[d]imidazol-2-imine (BTI), as a guest, to ethane-bridged bis(zinc octaethylporphyrin), bis(ZnOEP), as a host, has been studied by means of ultraviolet-visible (UV-Vis) and circular dichroism (CD) absorption spectroscopies, single crystal X-ray diffraction, and computa...

When an electron is removed from a halogen atom, it forms a halenium ion X⁺ (X = I, Br, Cl). In halogen bonding (XB), X⁺ is considered as a strong XB donor, and when interacting with two XB acceptors (e.g., pyridine), it forms a halonium XB complex with a [N–I–N] three-center-four-electron bond with the two XB acceptors. An unprecedented I⁺···Ag⁺ i...

Three‐dimensional aza‐analogues of 1,2‐benzothiazine 1,1‐dioxides have been prepared from sulfonimidamides. Two different protocols are presented. The first is a rhodium‐catalyzed annulation reaction with α ‐sulfonyloxyketones leading to 4‐unsubstituted benzothiazine derivatives. By selective bromination with NBS the heterocyclic ring can further b...

Construction of structurally complex architectures using inherently chiral, asymmetric, or multi-heterotopic ligands is a major challenge in metallosupramolecular chemistry. Moreover, the hierarchical self-organization of such complexes is unique. Here, we introduce a water-soluble, facially amphiphilic, amphoteric, chiral, asymmetric, and hetero-t...

A series of dumbbell-shaped sec-ammonium salts with bulky (pseudo)stoppers (‘speed bumps’) were tested for their ability to form pseudorotaxanes with a redox-switchable, tetrathiafulvalene (TTF)-decorated [24]crown-8 ether. Depending on the size...

A metalloorganic capsule was synthesized where the ligand is a derivative of heptazine with three carboxylic groups that are coordinated to CuII cations, forming paddle-wheel motifs. Each nanocapsule is neutral, with 12 CuII centers and 8 ligands adopting a rhombicuboctahedron shape. It has almost 3 nm diameter, and the main intermolecular interact...

Resorcinarenes are cavity‐containing compounds when in the crown conformation, from the calixarene family of concave compounds. These easy to synthesize macrocycles can be decorated at the upper rim through the eight hydroxyl groups and/or the 2‐position of the aromatic ring. They are good synthons in supramolecular chemistry leading to appealing a...

Assessment of the solution equilibria of [bis(pyridine)iodine(I)]⁺ complexes by ESI-MS and NMR reveals the preference of iodine(I) to form complexes with a more basic pyridine. Mixtures of symmetric [bis(pyridine)iodine(I)]⁺ complexes undergo statistical ligand exchange, with a predominant entropic driving force favoring asymmetric systems. The inf...

Ebselen (2-phenyl-1,2-benzoselenazol-3(2H)one), a glutathione peroxidase mimic, is active against several RNA viruses, among others the retrovirus responsible for the COVID-19 pandemic. In this paper ⁷⁷Se and ¹H NMR studies of ebselen are reported and they identify the chalcogen bond (ChB) and hydrogen bond (HB) that are central in the landscape of...

The synthesis of two series of gold(I) complexes containing the general formulae PR 3 -Au-C≡C-phenanthrene (PR 3 = PPh 3 ( 1a / 2a ), PMe 3 ( 1b / 2b ), PNaph 3 ( 1c / 2c )) or (diphos)(Au-C≡C-phenanthrene) 2 (diphos = 1,1- bis (diphenylphosphino)methane, dppm ( 1d / 2d ); 1,4- bis (diphenylphosphino)butane, dppb ( 1e / 2e )) have been synthesized....

In the presence of KOH, NH-sulfoximines react with pentafluoropyridine to give N-(tetrafluoropyridyl)sulfoximines (NTFP-sulfoximines) in moderate to excellent yields. Either a solution-based or a superior solvent-free mechanochemical protocol can be followed. X-Ray diffraction analyses of 26 products provided insight into the bond parameters and co...

Crown ethers are common building blocks in supramolecular chemistry and are frequently applied as cation sensors or as subunits in synthetic molecular machines. Developing switchable and specifically designed crown ethers enables the implementation of function into molecular assemblies. Seven tailor-made redox-active crown ethers incorporating tetr...

Five electron‐deficient aromatic compounds bearing 3,5‐bis(trifluoromethyl)benzyl moieties were investigated by X‐ray diffraction. In the crystals, the stacking of π systems between non‐planar electron‐deficient aromatics leads to an assembly with weak F···π and/or F···F interactions as the controlling factor. The stacking motifs of non‐planar elec...

The spin-spin interactions between unpaired electrons in organic (poly)radicals, especially nitroxides, are of largely inves-tigated and are of crucial importance for their applications in areas such as organic magnetism, molecular charge transfer or multiple spin labeling in structural biology. Recently, TEMPO and polymers functionalized with nitr...

A bis‐acridinium cyclophane incorporating switchable acridinium moieties linked by a 3,5‐dipyridylanisole spacer was studied as a multi‐responsive host for polycyclic aromatic hydrocarbon guests. Complexation of perylene was proven to be the most effective and was characterized in particular by a charge transfer band as signal output. Effective cat...

A bis‐acridinium cyclophane binds perylene selectively and reversibly upon chemical or redox stimuli in organic media. Its straightforward phase‐transfer into a perfluorocarbon was exploited for the enrichment of perylene from a mixture of polycyclic aromatic hydrocarbons (PAHs). Abstract A bis‐acridinium cyclophane incorporating switchable acridi...

A catalytic approach for the preparation of indolines by dearomatizing cyclization is presented. FeCl3 acts as a catalyst to afford tetracyclic 5a,6-dihydro-12H-indolo[2,1-b][1,3]benzoxazin-12-ones in good yields. The cyclization also proceeds with tosylamides forming C-N bonds in 53 % yield.

The new 2,3-secoiridoids morisecoiridoic acids A (1) and B (2), the new iridoid 8-acetoxyepishanzilactone (3), and four additional known iridoids (4–7) were isolated from the leaf and stem bark methanol extracts of Morinda asteroscepa using chromatographic methods. The structure of shanzilactone (4) was revised. The purified metabolites were identi...

A novel air‐stable PdI dimer is reported that triggers E‐selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups and with complete tolerance of air. The same dimer also triggers extremely rapid C−C coupling (alkylation and arylation) at room temperature in a modular and triply selective fashion....

Five new compounds—rhodimer (1), rhodiflavan A (2), rhodiflavan B (3), rhodiflavan C (4), and rhodacarpin (5)—along with 16 known secondary metabolites, were isolated from the CH2Cl2–CH3OH (1:1) extract of the roots of Tephrosia rhodesica. They were identified by NMR spectroscopic, mass spectrometric, X-ray crystallographic, and ECD spectroscopic a...

A study of the fluorescence enhancement of isoquinoline, acridine (benzo[b]quinoline) and benzo[h]quinoline is reported with six organic acids of different pKa values. Protonation was found to be an effective tool in the fluorescence enhancement of quinolines. A significant increase in the fluorescence intensity is observed only when strong acids a...

A new class of six mono- (1; 3-Cl-, 2; 5-Cl-, 3; 6-Cl-) and di-(4; 3,6-Cl, 5; 5,6-Cl-, 6; 3,5-Cl-) chloro-substituted pyrazin-2-amine ligands (1–6) form complexes with copper (I) bromide, to give 1D and 2D coordination polymers through a combination of halogen and hydrogen bonding that were characterized by X-ray diffraction analysis. These Cu(I) c...

At elevated temperatures, N-cyanosulfoximines react with Meldrum's acid derivatives to give sulfoximines with N-bound 5-carbonyl-1,3-oxazine-2,4-dione groups. A representative product was characterized by single-crystal X-ray structure analysis. The product formation involves an unexpected molecular reorientation requiring several sequential bond-f...

We report a new air‐stable Pd(I) dimer, i.e. [Pd(μ‐I)(PCy 2t Bu)] 2 that triggers E‐selective olefin migrations to enamides and styrene derivatives in the presence of multiple functional groups and under complete tolerance of air. The same dimer also triggers extremely rapid C‐C couplings (alkylation and arylation) at room temperature in a modular...

Mono‐ or biscatechol esters with ether‐type substituents or spacers form either triple lithium bridged dimeric helicates or triple stranded helicates with the ability to bind three lithium cations in their interior. Hierarchical helicates with ether or thioether substituents show in solution a monomer‐dimer equilibrium which is independent of the h...

The first asymmetric halogen-bonded iodonium complexes [I(py)(4-DMAP)]PF6 (2c) and [I(py)(4-Etpy)]PF6 (2e) were prepared via [N-Ag-N]+ -> [N-I-N]+ cation exchange of their analogous 2-coordinate silver complexes, strucurally characterised by 1H and...

The nature of C–I⋯⁻O–N⁺ interactions, first of its kind, between non-fluorinated tetraiodoethylene XB-donor and pyridine N-oxides (PyNO) are studied by single-crystal X-ray diffraction (SCXRD) and Density Functional Theory (DFT) calculations. Despite the non-fluorinated nature of the C2I4, the I⋯O halogen bond distances are similar to well-known pe...

2,2,2-Trifluoroethyl-substituted 3-oxazolines, 3-thiazolines, and 5,6-dihydro-2H-1,3-oxazines have been obtained by reacting substituted vinyl azides with a combination of Togni's reagent and substoichiometric amounts of iron(II) chloride. The results of density functional theory calculations support the proposed mechanism involving 1,n-hydrogen-at...

Induced fit and conformational selection are two dominant binding mechanisms in biology. Although induced fit has been widely accepted by supramolecular chemists, conformational selection is rarely studied with synthetic systems. In the present research, we report a macrocyclic host whose binding mechanism is unambiguously assigned to conformationa...

The synthesis of five novel cyclometalated platinum(II) compounds containing five different alkynyl-chromophores was achieved by the reaction of the previously synthesized Pt-Cl cyclometalated compound (1) with the corresponding RC≡CH by a Sonogashira reaction. It was observed that the spectral and photophysical characteristics of the cyclometalate...

Introducing biobased polymers from renewable sources for use as high-performance thermoplastics with high demands on mechanical rigidity, transparency, thermal stability, as well as good processability, is a significant challenge. In the present work we have designed and prepared a rigid biobased bis-spirocylic diol by di-cycloketalization of a bic...