Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

Chemical Reviews, Год журнала: 2018, Номер 119(3), С. 1855 - 1969

Опубликована: Дек. 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.

Язык: Английский

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Enantioselective Chemo‐ and Biocatalysis: Partners in Retrosynthesis

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(31), С. 8942 - 8973

Опубликована: Апрель 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.

Язык: Английский

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

Nature Catalysis, Год журнала: 2019, Номер 3(1), С. 48 - 54

Опубликована: Дек. 2, 2019

Язык: 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, Год журнала: 2017, Номер 139(12), С. 4443 - 4451

Опубликована: Март 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.

Язык: Английский

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Catalytic Asymmetric Umpolung Allylation of Imines

Journal of the American Chemical Society, Год журнала: 2016, Номер 138(40), С. 13103 - 13106

Опубликована: Сен. 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.

Язык: Английский

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

Chemical Society Reviews, Год журнала: 2018, Номер 47(8), С. 2772 - 2808

Опубликована: Янв. 1, 2018

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

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 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.

Язык: Английский

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

Organic Letters, Год журнала: 2017, Номер 19(12), С. 3219 - 3222

Опубликована: Май 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

Язык: Английский

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Enantioselektive Chemo‐ und Biokatalyse: Partner in der Retrosynthese

Angewandte Chemie, Год журнала: 2017, Номер 129(31), С. 9068 - 9100

Опубликована: Апрель 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, Год журнала: 2017, Номер 53(12), С. 1985 - 1988

Опубликована: Янв. 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.

Язык: Английский

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