Mikhail Kabeshov - Academia.edu (original) (raw)

Papers by Mikhail Kabeshov

Angewandte Chemie (International ed. in English), Jan 25, 2016

A continuous-flow synthesis of aziridines by palladium-catalyzed C(sp(3) )-H activation is descri... more A continuous-flow synthesis of aziridines by palladium-catalyzed C(sp(3) )-H activation is described. The new flow reaction could be combined with an aziridine-ring-opening reaction to give highly functionalized aliphatic amines through a consecutive process. A predictive mechanistic model was developed and used to design the C-H activation flow process and illustrates an approach towards first-principles design based on novel catalytic reactions.

Chemistry (Weinheim an der Bergstrasse, Germany), Jan 26, 2016

A short, nine-step, highly enantioselective synthesis of (-)-erogorgiaene and its C-11 epimer is ... more A short, nine-step, highly enantioselective synthesis of (-)-erogorgiaene and its C-11 epimer is reported. The key stereochemistry controlling steps involve catalytic asymmetric crotylation, anionic oxy-Cope rearrangement and cationic cyclisation. (-)-Erogorgiaene exhibited promising antitubercular activity against multidrug-resistant strains of Mycobacterium tuberculosis.

Angewandte Chemie (International ed. in English), Jan 6, 2016

We report herein a new method for the photoredox activation of boronic esters. Using these reagen... more We report herein a new method for the photoredox activation of boronic esters. Using these reagents, an efficient and high-throughput continuous flow process was developed to perform a dual iridium- and nickel-catalyzed C(sp(2) )-C(sp(3) ) coupling by circumventing solubility issues associated with potassium trifluoroborate salts. Formation of an adduct with a pyridine-derived Lewis base was found to be essential for the photoredox activation of the boronic esters. Based on these results we were able to develop a further simplified visible light mediated C(sp(2) )-C(sp(3) ) coupling method using boronic esters and cyano heteroarenes under flow conditions.

Org Lett, 2007

Leucinol and valinol have been identified as efficient organocatalysts for the aldol reaction of ... more Leucinol and valinol have been identified as efficient organocatalysts for the aldol reaction of isatin and its derivatives (as examples of activated, non-enolizable ketones) with acetone. Uncommon mechanistic features were observed and used in the formulation of the transition state of the reaction.

Synlett, 2010

... Direct Preparation of Heteroaromatic Compounds from Alkenes. Timothy J. Donohoe* a , Mikhail ... more ... Direct Preparation of Heteroaromatic Compounds from Alkenes. Timothy J. Donohoe* a , Mikhail A. Kabeshov a,b , Akshat H. Rathi a , Ian ED Smith b. ... 9 Evans RD, Herman J,Synthesis 1986, 727. 10a Yadav JS, Reddy BVS, Singh AP, Basak AK,Tetrahedron Lett. 2008, 49: 5880. ...

Computational and Theoretical Chemistry, 2016

Chemistry - A European Journal, 2015

Chemistry (Weinheim an der Bergstrasse, Germany), Jan 6, 2015

Comprehensive mechanistic studies on the enantioselective aldol reaction between isatin (1 a) and... more Comprehensive mechanistic studies on the enantioselective aldol reaction between isatin (1 a) and acetone, catalyzed by L-leucinol (3 a), unraveled that isatin, apart from being a substrate, also plays an active catalytic role. Conversion of the intermediate oxazolidine 4 into the reactive syn-enamine 6, catalyzed by isatin, was identified as the rate-determining step by both the calculations (ΔG(≠) =26.1 kcal mol(-1) for the analogous L-alaninol, 3 b) and the kinetic isotope effect (kH /kD =2.7 observed for the reaction using [D6 ]acetone). The subsequent reaction of the syn-enamine 6 with isatin produces (S)-2 a (calculated ΔG(≠) =11.6 kcal mol(-1) ). The calculations suggest that the overall stereochemistry is controlled by two key events: 1) the isatin-catalyzed formation of the syn-enamine 6, which is thermodynamically favored over its anti-rotamer 7 by 2.3 kcal mol(-1) ; and 2) the high preference of the syn-enamine 6 to produce (S)-2 a on reaction with isatin (1 a) rather tha...

Chem. Commun., 2015

A novel integrated web-based system which can compute, visualise and store systematised key param... more A novel integrated web-based system which can compute, visualise and store systematised key parameters of a reaction has been developed from open-source components. As a proof of concept, it has been used to rationalise and predict the regioselectivity of lithiation reactions as well as relative reactivity of substrates. Excellent agreement between the in silico analysis and experimental data was obtained.

Organic letters, Jan 5, 2014

An expedient synthesis of the indole alkaloid nazlinine is reported. Judicious choice of flow ele... more An expedient synthesis of the indole alkaloid nazlinine is reported. Judicious choice of flow electrochemistry as an enabling technology has permitted the rapid generation of a small library of unnatural relatives of this biologically active molecule. Furthermore, by conducting the key electrochemical Shono oxidation in a flow cell, the loading of electrolyte can be significantly reduced to 20 mol % while maintaining a stable, broadly applicable process.

ChemInform, 2009

We have found that ligand control over the carbon-carbon and carbon-heteroatom bond formation on ... more We have found that ligand control over the carbon-carbon and carbon-heteroatom bond formation on the nickel center provides an easy and convenient route to symmetrical (minor) and unsymmetrical (major) isomers of sulfur-and selenium-substituted 1,3-dienes. The unsymmetrical product is a new type of 1,4-substituted conjugated diene, which was readily synthesized from alkynes and diaryldichalcogenides. The unique feature of this developed one-pot transformation is total stereodefined synthesis of the diene skeleton, controlling not only the configuration of the double bond but also the s-gauche conformation of the central C-C bond. The mechanistic study revealed the key feature of alkyne insertion into the Ni-E and Ni-C bonds (E ) S, Se), which governs the direction of the chemical transformation. Lee, J.; Cho, M.; Sheares, V. V. Macromolecules 2006, 39, 8625. (f) Beery, M. D.; Rath, M. K.; Sheares, V. V. Macromolecules 2001, 34, 2469. a Conditions: toluene, 70°C, 3 h, 3 mol % Ni(acac)2, and 30 mol % L. b Reaction time 1 h.

Chemistry - A European Journal, 2015

A new, highly efficient Lewis base catalyst for a practical enantio- and diastereoselective croty... more A new, highly efficient Lewis base catalyst for a practical enantio- and diastereoselective crotylation of unsaturated aldehydes with E- and Z-crotyltrichlorosilanes has been developed. The method was employed as a key step in a novel asymmetric synthesis of bioactive serrulatane diterpene (-)-elisabethadione. Other strategic reactions for setting up the stereogenic centers included anionic oxy-Cope rearrangement and cationic cyclization. The synthetic route relies on simple, high yielding reactions and avoids use of protecting groups or chiral auxiliaries.

ChemInform, 2011

Direct Preparation of Heteroaromatic Compounds from Alkenes. -Aromatic heterocycles, such as thia... more Direct Preparation of Heteroaromatic Compounds from Alkenes. -Aromatic heterocycles, such as thiazoles (III), imidazoles (V) and indole derivative (VII) are synthesized directly from alkenes (I) via a ketoiodination-cyclization protocol. The heterocycles are formed in good yields and with high regioselectivity. -(DONOHOE*, T. J.; KABESHOV, M. A.; RATHI, A. H.; SMITH, I. E. D.; Synlett 2010, 19, 2956-2958, http://dx.doi.org/10.1055/s-0030-1259034 ; Dep. Chem., Univ. Oxford, Oxford OX1 3TA, UK; Eng.) -M. Paetzel

ChemInform, 2009

Enantioselective and Catalytic Method for α-Crotylation of Aldehydes with a Kinetic Self-Refineme... more Enantioselective and Catalytic Method for α-Crotylation of Aldehydes with a Kinetic Self-Refinement of Stereochemistry. -A practical, highly stereoselective protocol is developed. In each step, one of the stereoisomers reacts faster than the other, what results in a kinetic stereochemical (E/Z) self-refinement of the system and leads to the formation of virtually enantiomerically and geometrically pure linear homoallylic alcohols. -(MALKOV*, A. V.; KABESHOV, M. A.; BARLOG, M.; KOCOVSKY, P.; Chem. Eur. J. 15 (2009) 7, 1570-1573; Dep. Chem.,

Journal of Molecular Structure, 2014

ABSTRACT Herein we describe structural insights of (5Z)-3-benzyl-5-(2-fluorobenzylidene)furan-2(5... more ABSTRACT Herein we describe structural insights of (5Z)-3-benzyl-5-(2-fluorobenzylidene)furan-2(5H)-one (6) and (5Z)-3-benzyl-5-(pentafluorobenzylidene)furan-2(5H)-one (7), gamma-alkylidenebutenolides analogues of the natural products nostoclides. Their structures were investigated by NMR spectroscopy and X-ray crystallography. The stereochemistry of the exocyclic double bond of these fluorinated compounds was determined to be Z by NMR analysis and confirmed by X-ray data. Compounds 6 and 7 crystallized in the monoclinic crystal system P2(1)/c group. A comparison between structural features of (6) and (7) and nostoclide derivatives previously published by us is described. (C) 2014 Published by Elsevier B.V.

ChemInform, 2011

Exerting Control over the Acyloin Reaction. -The acyloin reaction of unsymmetrical diesters (V) l... more Exerting Control over the Acyloin Reaction. -The acyloin reaction of unsymmetrical diesters (V) leads regioselectively to derivatives (VI) in good yields. Acyloin (VIc) is used as convenient starting compound for the synthesis of diols (VII) and (IX), thiazole (XI), and indole (XIII). -(DONOHOE*, T. J.; JAHANSHAHI, A.; TUCKER, M. J.; BHATTI, F. L.; ROSLAN, I. A.; KABESHOV, M.; WRIGLEY, G.; Chem. Commun. (Cambridge) 47 (2011) 20, 5849-5851, http://dx.doi.org/10.1039/c1cc11654a ; Chem. Res. Lab., Dep. Chem., Univ. Oxford, Oxford OX1 3TA, UK; Eng.) -R. Staver 34-026

Angewandte Chemie (International ed. in English), Jan 25, 2016

A continuous-flow synthesis of aziridines by palladium-catalyzed C(sp(3) )-H activation is descri... more A continuous-flow synthesis of aziridines by palladium-catalyzed C(sp(3) )-H activation is described. The new flow reaction could be combined with an aziridine-ring-opening reaction to give highly functionalized aliphatic amines through a consecutive process. A predictive mechanistic model was developed and used to design the C-H activation flow process and illustrates an approach towards first-principles design based on novel catalytic reactions.

Chemistry (Weinheim an der Bergstrasse, Germany), Jan 26, 2016

A short, nine-step, highly enantioselective synthesis of (-)-erogorgiaene and its C-11 epimer is ... more A short, nine-step, highly enantioselective synthesis of (-)-erogorgiaene and its C-11 epimer is reported. The key stereochemistry controlling steps involve catalytic asymmetric crotylation, anionic oxy-Cope rearrangement and cationic cyclisation. (-)-Erogorgiaene exhibited promising antitubercular activity against multidrug-resistant strains of Mycobacterium tuberculosis.

Angewandte Chemie (International ed. in English), Jan 6, 2016

We report herein a new method for the photoredox activation of boronic esters. Using these reagen... more We report herein a new method for the photoredox activation of boronic esters. Using these reagents, an efficient and high-throughput continuous flow process was developed to perform a dual iridium- and nickel-catalyzed C(sp(2) )-C(sp(3) ) coupling by circumventing solubility issues associated with potassium trifluoroborate salts. Formation of an adduct with a pyridine-derived Lewis base was found to be essential for the photoredox activation of the boronic esters. Based on these results we were able to develop a further simplified visible light mediated C(sp(2) )-C(sp(3) ) coupling method using boronic esters and cyano heteroarenes under flow conditions.

Org Lett, 2007

Leucinol and valinol have been identified as efficient organocatalysts for the aldol reaction of ... more Leucinol and valinol have been identified as efficient organocatalysts for the aldol reaction of isatin and its derivatives (as examples of activated, non-enolizable ketones) with acetone. Uncommon mechanistic features were observed and used in the formulation of the transition state of the reaction.

Synlett, 2010

... Direct Preparation of Heteroaromatic Compounds from Alkenes. Timothy J. Donohoe* a , Mikhail ... more ... Direct Preparation of Heteroaromatic Compounds from Alkenes. Timothy J. Donohoe* a , Mikhail A. Kabeshov a,b , Akshat H. Rathi a , Ian ED Smith b. ... 9 Evans RD, Herman J,Synthesis 1986, 727. 10a Yadav JS, Reddy BVS, Singh AP, Basak AK,Tetrahedron Lett. 2008, 49: 5880. ...

Computational and Theoretical Chemistry, 2016

Chemistry - A European Journal, 2015

Chemistry (Weinheim an der Bergstrasse, Germany), Jan 6, 2015

Comprehensive mechanistic studies on the enantioselective aldol reaction between isatin (1 a) and... more Comprehensive mechanistic studies on the enantioselective aldol reaction between isatin (1 a) and acetone, catalyzed by L-leucinol (3 a), unraveled that isatin, apart from being a substrate, also plays an active catalytic role. Conversion of the intermediate oxazolidine 4 into the reactive syn-enamine 6, catalyzed by isatin, was identified as the rate-determining step by both the calculations (ΔG(≠) =26.1 kcal mol(-1) for the analogous L-alaninol, 3 b) and the kinetic isotope effect (kH /kD =2.7 observed for the reaction using [D6 ]acetone). The subsequent reaction of the syn-enamine 6 with isatin produces (S)-2 a (calculated ΔG(≠) =11.6 kcal mol(-1) ). The calculations suggest that the overall stereochemistry is controlled by two key events: 1) the isatin-catalyzed formation of the syn-enamine 6, which is thermodynamically favored over its anti-rotamer 7 by 2.3 kcal mol(-1) ; and 2) the high preference of the syn-enamine 6 to produce (S)-2 a on reaction with isatin (1 a) rather tha...

Chem. Commun., 2015

A novel integrated web-based system which can compute, visualise and store systematised key param... more A novel integrated web-based system which can compute, visualise and store systematised key parameters of a reaction has been developed from open-source components. As a proof of concept, it has been used to rationalise and predict the regioselectivity of lithiation reactions as well as relative reactivity of substrates. Excellent agreement between the in silico analysis and experimental data was obtained.

Organic letters, Jan 5, 2014

An expedient synthesis of the indole alkaloid nazlinine is reported. Judicious choice of flow ele... more An expedient synthesis of the indole alkaloid nazlinine is reported. Judicious choice of flow electrochemistry as an enabling technology has permitted the rapid generation of a small library of unnatural relatives of this biologically active molecule. Furthermore, by conducting the key electrochemical Shono oxidation in a flow cell, the loading of electrolyte can be significantly reduced to 20 mol % while maintaining a stable, broadly applicable process.

ChemInform, 2009

We have found that ligand control over the carbon-carbon and carbon-heteroatom bond formation on ... more We have found that ligand control over the carbon-carbon and carbon-heteroatom bond formation on the nickel center provides an easy and convenient route to symmetrical (minor) and unsymmetrical (major) isomers of sulfur-and selenium-substituted 1,3-dienes. The unsymmetrical product is a new type of 1,4-substituted conjugated diene, which was readily synthesized from alkynes and diaryldichalcogenides. The unique feature of this developed one-pot transformation is total stereodefined synthesis of the diene skeleton, controlling not only the configuration of the double bond but also the s-gauche conformation of the central C-C bond. The mechanistic study revealed the key feature of alkyne insertion into the Ni-E and Ni-C bonds (E ) S, Se), which governs the direction of the chemical transformation. Lee, J.; Cho, M.; Sheares, V. V. Macromolecules 2006, 39, 8625. (f) Beery, M. D.; Rath, M. K.; Sheares, V. V. Macromolecules 2001, 34, 2469. a Conditions: toluene, 70°C, 3 h, 3 mol % Ni(acac)2, and 30 mol % L. b Reaction time 1 h.

Chemistry - A European Journal, 2015

A new, highly efficient Lewis base catalyst for a practical enantio- and diastereoselective croty... more A new, highly efficient Lewis base catalyst for a practical enantio- and diastereoselective crotylation of unsaturated aldehydes with E- and Z-crotyltrichlorosilanes has been developed. The method was employed as a key step in a novel asymmetric synthesis of bioactive serrulatane diterpene (-)-elisabethadione. Other strategic reactions for setting up the stereogenic centers included anionic oxy-Cope rearrangement and cationic cyclization. The synthetic route relies on simple, high yielding reactions and avoids use of protecting groups or chiral auxiliaries.

ChemInform, 2011

Direct Preparation of Heteroaromatic Compounds from Alkenes. -Aromatic heterocycles, such as thia... more Direct Preparation of Heteroaromatic Compounds from Alkenes. -Aromatic heterocycles, such as thiazoles (III), imidazoles (V) and indole derivative (VII) are synthesized directly from alkenes (I) via a ketoiodination-cyclization protocol. The heterocycles are formed in good yields and with high regioselectivity. -(DONOHOE*, T. J.; KABESHOV, M. A.; RATHI, A. H.; SMITH, I. E. D.; Synlett 2010, 19, 2956-2958, http://dx.doi.org/10.1055/s-0030-1259034 ; Dep. Chem., Univ. Oxford, Oxford OX1 3TA, UK; Eng.) -M. Paetzel

ChemInform, 2009

Enantioselective and Catalytic Method for α-Crotylation of Aldehydes with a Kinetic Self-Refineme... more Enantioselective and Catalytic Method for α-Crotylation of Aldehydes with a Kinetic Self-Refinement of Stereochemistry. -A practical, highly stereoselective protocol is developed. In each step, one of the stereoisomers reacts faster than the other, what results in a kinetic stereochemical (E/Z) self-refinement of the system and leads to the formation of virtually enantiomerically and geometrically pure linear homoallylic alcohols. -(MALKOV*, A. V.; KABESHOV, M. A.; BARLOG, M.; KOCOVSKY, P.; Chem. Eur. J. 15 (2009) 7, 1570-1573; Dep. Chem.,

Journal of Molecular Structure, 2014

ABSTRACT Herein we describe structural insights of (5Z)-3-benzyl-5-(2-fluorobenzylidene)furan-2(5... more ABSTRACT Herein we describe structural insights of (5Z)-3-benzyl-5-(2-fluorobenzylidene)furan-2(5H)-one (6) and (5Z)-3-benzyl-5-(pentafluorobenzylidene)furan-2(5H)-one (7), gamma-alkylidenebutenolides analogues of the natural products nostoclides. Their structures were investigated by NMR spectroscopy and X-ray crystallography. The stereochemistry of the exocyclic double bond of these fluorinated compounds was determined to be Z by NMR analysis and confirmed by X-ray data. Compounds 6 and 7 crystallized in the monoclinic crystal system P2(1)/c group. A comparison between structural features of (6) and (7) and nostoclide derivatives previously published by us is described. (C) 2014 Published by Elsevier B.V.

ChemInform, 2011

Exerting Control over the Acyloin Reaction. -The acyloin reaction of unsymmetrical diesters (V) l... more Exerting Control over the Acyloin Reaction. -The acyloin reaction of unsymmetrical diesters (V) leads regioselectively to derivatives (VI) in good yields. Acyloin (VIc) is used as convenient starting compound for the synthesis of diols (VII) and (IX), thiazole (XI), and indole (XIII). -(DONOHOE*, T. J.; JAHANSHAHI, A.; TUCKER, M. J.; BHATTI, F. L.; ROSLAN, I. A.; KABESHOV, M.; WRIGLEY, G.; Chem. Commun. (Cambridge) 47 (2011) 20, 5849-5851, http://dx.doi.org/10.1039/c1cc11654a ; Chem. Res. Lab., Dep. Chem., Univ. Oxford, Oxford OX1 3TA, UK; Eng.) -R. Staver 34-026