Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(3), P. 1855 - 1969

Published: Dec. 24, 2018

In this review, we summarize the origin and advancements of iridium-catalyzed asymmetric allylic substitution reactions during past two decades. Since first report in 1997, Ir-catalyzed have attracted intense attention due to their exceptionally high regio- enantioselectivities. been significantly developed recent years many respects, including ligand development, mechanistic understanding, substrate scope, application synthesis complex functional molecules. an explicit outline ligands, mechanism, scope nucleophiles, applications is presented.

Language: Английский

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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 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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Synergistic Dual Transition Metal Catalysis

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(24), P. 13382 - 13433

Published: Nov. 29, 2020

Synergistic catalysis, a type of plural catalysis which utilizes at least two different catalysts to enable reaction between separately activated substrates, has unlocked plethora previously unattainable transformations and novel chemical reactivity. Despite the appreciable utility synergistic specific examples involving transition metals have been limited, as ensuring judicious choice parameters prevent deactivation catalysts, undesirable monocatalytic event(s) leading side products, or premature termination other potentially troublesome outcomes present formidable challenge. Excluding those driven by photocatalytic mechanisms, this review will highlight reported reactions that make use simultaneous catalytic cycles metal catalysts.

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 Aldehydes and Alkynes via Synergistic Catalysis Using Rh and Jacobsen’s Amine

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(3), P. 1029 - 1032

Published: Jan. 11, 2017

We report an enantioselective coupling between α-branched aldehydes and alkynes to generate vicinal quaternary tertiary carbon stereocenters. The choice of Rh organocatalyst combination allows for access all possible stereoisomers with high enantio-, diastereo-, regioselectivity. Our study highlights the power catalysis activate two common functional groups provide divergent constitutional structures.

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 Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(4), P. 1239 - 1242

Published: Jan. 10, 2018

We report stereodivergent allylic substitution reactions of esters with prochiral enolates derived from azaaryl acetamides and acetates to form products addition the at most substituted carbon an allyl moiety two catalysts, a chiral metallacyclic iridium complex bisphosphine-ligated copper(I) complex, which individually control configuration electrophilic nucleophilic atoms, respectively. By simple permutations enantiomers all four stereoisomers containing stereogenic centers were synthesized high diastereoselectivity enantioselectivity. A variety bearing pyridyl, benzothiazolyl, benzoxazolyl, pyrazinyl, quinolinyl isoquinolinyl moieties found be suitable for this transformation.

Language: Английский

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Stereoselective and Site-Specific Allylic Alkylation of Amino Acids and Small Peptides via a Pd/Cu Dual Catalysis

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(29), P. 9819 - 9822

Published: July 7, 2017

We report a stereoselective and site-specific allylic alkylation of Schiff base activated amino acids small peptides via Pd/Cu dual catalysis. A range noncoded α,α-dialkyl α-amino were easily synthesized in high yields with excellent enantioselectivities (up to >99% ee). Furthermore, direct highly synthesis enantiopure α-alkyl or residues incorporated at specific sites was accomplished using this catalyst system.

Language: Английский

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