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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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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Diastereodivergent synthesis of enantioenriched α,β-disubstituted γ-butyrolactones via cooperative N-heterocyclic carbene and Ir catalysis

Nature Catalysis, Journal Year: 2019, Volume and Issue: 3(1), P. 48 - 54

Published: Dec. 2, 2019

Language: Английский

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Mechanistic Studies on a Cooperative NHC Organocatalysis/Palladium Catalysis System: Uncovering Significant Lessons for Mixed Chiral Pd(NHC)(PR₃) Catalyst Design

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(12), P. 4443 - 4451

Published: March 6, 2017

A comprehensive investigation of the mechanism highly enantioselective Pd(PPh3)4/NHC-catalyzed annulation vinyl benzoxazinanones and enals has been conducted. study reaction orders supports postulated cooperative catalysis. Interestingly, a detailed catalytically active palladium species pointed toward dual role NHC acting as an organocatalyst forming novel mixed ligand Pd/NHC/phosphine complex. The complex represents new class chiral catalyst. Remarkably, phosphine plays crucial in this transformation. These complexes could be characterized by X-ray crystallographic analysis employed catalysts for [4 + 1] benzoxazinones sulfur ylides good yields enantioselectivities.

Language: Английский

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Catalytic Asymmetric Umpolung Allylation of Imines

Journal of the American Chemical Society, Journal Year: 2016, Volume and Issue: 138(40), P. 13103 - 13106

Published: Sept. 19, 2016

Here we report an iridium-catalyzed asymmetric umpolung allylation of imines as a general approach to prepare 1,4-disubstituted homoallylic amines, fundamental class compounds that are hitherto not straightforward obtain. This transformation proceeds by cascade involving intermolecular regioselective 2-azaallyl anions and following 2-aza-Cope rearrangement, utilizes easily available reagents catalysts, tolerates substantial scope substrates, readily leads various enantioenriched, primary amines.

Language: Английский

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A leap forward in iridium–NHC catalysis: new horizons and mechanistic insights

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(8), P. 2772 - 2808

Published: Jan. 1, 2018

Ir–NHC catalysts have been crucial to the advance of an ever-growing diversity processes thanks their prolific reactivity and mechanistic flexibility.

Language: Английский

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Direct Catalytic Asymmetric and Regiodivergent N1‐ and C3‐Allenylic Alkylation of Indoles

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 21, 2023

Herein we report a Pd-catalyzed asymmetric allenylic alkylation strategy for the direct functionalization of 1H-indoles by employing P-chiral BIBOP-type ligands. The regioselectivity (N1/C3) this process can be switched efficiently. Using Cs2 CO3 at elevated temperatures in MeCN, N1-alkylated indoles bearing axial chirality with stereocenter non-adjacent (β) to nitrogen are produced good yields high enantioselectivity and complete N1-regioselectivity regardless electronic properties substitution patterns diverse indoles. K2 room temperature CH2 Cl2 , chiral C3-alkylated also obtained. Notably, introduce new class tri-substituted electrophiles that proceeded through different pathways from di-substituted electrophiles.

Language: Английский

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Catalytic Asymmetric Construction of the Tryptanthrin Skeleton via an Enantioselective Decarboxylative [4 + 2] Cyclization

Organic Letters, Journal Year: 2017, Volume and Issue: 19(12), P. 3219 - 3222

Published: May 25, 2017

The first catalytic asymmetric construction of the tryptanthrin skeleton has been established, taking advantage a palladium(0)/chiral ligand-catalyzed enantioselective decarboxylative [4 + 2] cyclization vinyl benzoxazinanones with isatins. This reaction not only provided direct and efficient method for constructing chiral skeleta in high yields excellent enantioselectivities (up to 97% yield, >99% ee) but also represents

Language: Английский

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Enantioselektive Chemo‐ und Biokatalyse: Partner in der Retrosynthese

Angewandte Chemie, Journal Year: 2017, Volume and Issue: 129(31), P. 9068 - 9100

Published: April 13, 2017

Abstract In diesem Aufsatz werden neue Entwicklungen auf den Gebieten der biokatalytischen und chemokatalytischen Synthese diskutiert. Der Beitrag soll als Anleitung für die Verwendung biokatalytischer Methoden in chemischen dienen, insbesondere bei retrosynthetischen Überlegungen Analysen. Die Gliederung dieses Aufsatzes ist nach Bindungsknüpfungen ihren jeweiligen synthetischen strukturiert.

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Ir/PTC cooperatively catalyzed asymmetric umpolung allylation of α-imino ester enabled synthesis of α-quaternary amino acid derivatives bearing two vicinal stereocenters

Chemical Communications, Journal Year: 2017, Volume and Issue: 53(12), P. 1985 - 1988

Published: Jan. 1, 2017

A novel Ir/PTC (phase-transfer catalyst) cooperatively catalyzed asymmetric umpolung allylation of simple α-imino esters is developed and it provides facile access to α-quaternary amino acid derivatives bearing two vicinal stereocenters.

Language: Английский

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