Stereodivergence in Asymmetric Catalysis

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(16), P. 5627 - 5639

Published: April 6, 2017

This Perspective presents an overview of catalytic enantioselective transformations that allow convenient access to all stereoisomers a given product with multiple stereogenic centers. Particular focus is placed on discussion the concept stereodivergent dual catalysis and its application in target-oriented synthesis. The potential this development new as well implications for achieving stereochemical diversity library design diversity-oriented synthesis are also discussed.

Language: Английский

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Stereodivergent Catalysis

Chemical Reviews, Journal Year: 2018, Volume and Issue: 118(10), P. 5080 - 5200

Published: April 20, 2018

This review covers diastereo- and enantiodivergent catalyzed reactions in acyclic cyclic systems using metal complexes or organocatalysts. Among them, nucleophilic addition to carbon–carbon carbon–nitrogen double bonds, α-functionalization of carbonyl compounds, allylic substitutions, ring opening oxiranes aziridines are considered. The diastereodivergent synthesis alkenes from alkynes is also included. Finally, stereodivergent intramolecular intermolecular cycloadditions other cyclizations reported.

Language: Английский

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Acyclic Quaternary Carbon Stereocenters via Enantioselective Transition Metal Catalysis

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(19), P. 12564 - 12580

Published: Sept. 14, 2017

Whereas numerous asymmetric methods for formation of quaternary carbon stereocenters in cyclic systems have been documented, the construction acyclic with control absolute stereochemistry remains a formidable challenge. This Review summarizes enantioselective from achiral or chiral racemic reactants via transition metal catalysis.

Language: Английский

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Asymmetric synthesis of allylic compoundsviahydrofunctionalisation and difunctionalisation of dienes, allenes, and alkynes

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(7), P. 2060 - 2118

Published: Jan. 1, 2020

This review article provides an overview of progress in asymmetric synthesis allylic compoundsviahydrofunctionalisation and difunctionalisation dienes, allenes, alkynes.

Language: Английский

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Stereodivergent Synthesis of α,α-Disubstituted α-Amino Acids via Synergistic Cu/Ir Catalysis

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(4), P. 1508 - 1513

Published: Jan. 5, 2018

Cu/Ir dual catalysis has been developed for the stereodivergent α-allylation of aldimine esters. The method enables preparation a series nonproteinogenic α-amino acids (α-AAs) bearing two contiguous stereogenic centers in high yield with excellent stereoselectivity. All four product stereoisomers could be obtained from same set starting materials via pairwise combination chiral catalysts. Notably, one-pot protocol successfully applied bimetallic complexes to simplify manipulation catalysis. This further utilized construction key intermediate bioactive pyrrolidine derivative and concise synthesis plant growth regulator (2S,3S)-2-amino-3-cyclopropylbutanoic acid.

Language: Английский

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Ir/Cu Dual Catalysis: Enantio- and Diastereodivergent Access to α,α-Disubstituted α-Amino Acids Bearing Vicinal Stereocenters

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(6), P. 2080 - 2084

Published: Jan. 30, 2018

We describe a fully stereodivergent synthesis of range α,α-disubstituted α-amino acids via an Ir/Cu-catalyzed α-allylation readily available imine esters. The introduction Cu-Phox complex-activated ester into the chiral iridium-catalyzed allylic allylation process is crucial for its high reactivity and excellent enantio- diastereoselectivity (up to >99% ee >20:1 dr). Importantly, two catalysts allow full control over configuration stereocenters, affording all stereoisomers desired products. utility this methodology was demonstrated by synthesizing dipeptides analogues bioactive molecules in manner.

Language: Английский

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Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(31), P. 8942 - 8973

Published: April 13, 2017

Abstract Recent developments of stereoselective biocatalytic and chemocatalytic methods are discussed. The review provides a guide to the use in area chemical synthesis with focused attention on retrosynthetic considerations analysis. transformations presented organized according bond disconnections attendant synthetic methods. is expected lead better understanding characteristics distinctions two complementary approaches. It depicts for researchers bio‐ chemocatalysis road map challenges opportunities evolution (and at times revolution) synthesis.

Language: Английский

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Stereodivergent Coupling of 1,3-Dienes with Aldimine Esters Enabled by Synergistic Pd and Cu Catalysis

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(37), P. 14554 - 14559

Published: Sept. 3, 2019

Herein we describe the use of synergistic Pd and Cu catalysis for stereodivergent coupling reactions between 1,3-dienes aldimine esters. By using different enantiomers two metal catalysts, all four stereoisomers products, which have vicinal stereocenters, could be accessed with high diastereo- enantioselectivity. This atom-economical cross-coupling reaction has a wide substrate scope good functional group tolerance. Our work highlights power asymmetric involving Pd-hydride catalysts.

Language: Английский

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Stereodivergent Construction of Tertiary Fluorides in Vicinal Stereogenic Pairs by Allylic Substitution with Iridium and Copper Catalysts

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(33), P. 13066 - 13073

Published: July 25, 2019

Although much effort has been spent on the enantioselective synthesis of tertiary alkyl fluorides, compounds containing such a stereogenic center within an array stereocenters, particularly two vicinal ones, remains synthetic challenge, and no method to control configuration each independently reported. We describe strategy achieve stereodivergent centers, one fluorine atom, by forming connecting carbon-carbon bond with catalyst system comprising iridium complex that controls at electrophilic carbon copper nucleophilic fluorine-containing carbon. These reactions occur alkyl- aryl-substituted allylic esters unstabilized enolates azaaryl ketones, esters, amides in high yield, diastereoselectivity, enantioselectivity (generally >90% >20:1 dr, 97-99% ee). Access all four stereoisomers products demonstrates precise configurations independently. This methodology extends construction quaternary stereocenters similarly yield selectivity. DFT calculations uncover origin stereoselectivity enolate substitution.

Language: Английский

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Stereodivergent Synthesis of Tetrahydrofuroindoles through Pd‐Catalyzed Asymmetric Dearomative Formal [3+2] Cycloaddition

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(8), P. 2134 - 2138

Published: Jan. 13, 2018

A stereodivergent synthesis of tetrahydrofuroindoles through palladium-catalyzed asymmetric dearomative formal [3+2] cycloaddition nitroindoles with epoxybutenes was developed. The polarity the solvent found to play a key role in diastereoselectivity. In toluene, good excellent yields (70-99 %), diastereoselectivity (87/13->95/5 d.r.), and enantioselectivity (85/15-94/6 e.r.) were obtained, regardless properties substituents on nitroindoles. acetonitrile, different diastereoisomer produced (75-98 %) stereoselectivity (78/22-93/7 d.r., 93/7-99/1 e.r.). Mechanistic studies conducted illustrate origin diastereodivergency. kinetic experiments indicate that rate-determining step this reaction is solvents. ESI-MS also support existence palladium complex intermediates catalytic cycle reaction.

Language: Английский

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