Stereodivergent Propargylic Alkylation of Enals via Cooperative NHC and Copper Catalysis DOI Creative Commons

Yu‐Hua Wen,

Zijing Zhang, Shuai Li

и другие.

Research Square (Research Square), Год журнала: 2021, Номер unknown

Опубликована: Авг. 13, 2021

Abstract Despite that asymmetric stereodivergent synthesis has experienced great success to provide unusual processes for the creation of chirality complexity, concepts appliable catalysis are still limited. The dependence on capacity each catalyst precisely control reactive site planar in region poses unparalleled constraint this field. Here, we first demonstrate chiral Cu-allenylidene species can participate propargylic alkylation enals, concert with N-heterocyclic carbenes (NHCs). Thus, all four stereoisomers were obtained excellent enantioselectivity and diastereoselectivity (up >99% e.e. >95:5 d.r.) from same starting materials by simply altering Cu-Pybox complex NHC combinations. rich chemistry workable products enables structurally diverse functional molecules holds potential alkaloid synthesis, as showcased preparation key building block access (-)-perophpramidine.

Язык: Английский

Asymmetric Redox Allylic Alkylation to Access 3,3′‐Disubstituted Oxindoles Enabled by Ni/NHC Cooperative Catalysis DOI

Tao Fan,

Jin Song, Liu‐Zhu Gong

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(22)

Опубликована: Март 3, 2022

The feasibility of cooperative catalysis between chiral N-heterocyclic carbenes and nickel in asymmetric reactions has been demonstrated convincingly. high efficiency this catalytic system enables the allylic alkylation isatin-derived enals with carbonates [3+3] annulation racemic vinyl epoxides to provide straightforward access highly enantioenriched 3,3'-disubstituted oxindoles. great practicality method organic synthesis showcased by facile product modification enantioselective key building block (-)-debromoflustramine B.

Язык: Английский

Процитировано

48
Enantioselective Cascade Annulation of α‐Amino‐ynones and Enals Enabled by Gold and Oxidative NHC Relay Catalysis DOI

Jianfeng Jiang,

Xia Wang, Shengping Liu

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(13)

Опубликована: Янв. 14, 2022

We report herein an unprecedented gold and oxidative NHC relay catalysis that enables highly enantioselective cascade annulation between readily available α-amino-ynones with enals. This method utilizes the in situ-generated pyrrolin-4-ones as a novel versatile synthon, which engage α,β-unsaturated acylazolium intermediates generated from enals by to produce pyrrole-fused lactones high yield excellent enantioselectivity. Synthetic utility of lactone products is also demonstrated facile conversion densely functionalized pyrroles yields stereopurity.

Язык: Английский

Процитировано

28
Enantioselective Synthesis of Spiro Heterocyclic Compounds Using a Combination of Organocatalysis and Transition‐Metal Catalysis DOI Creative Commons
Martin Kamlar, Michal Urban, Ján Veselý

и другие.

The Chemical Record, Год журнала: 2023, Номер 23(7)

Опубликована: Янв. 26, 2023

Abstract Over the last ten years, combination of organocatalysis with transition metal (TM) catalysis has become one most important toolboxes used for synthesizing optically pure compounds containing chiral quaternary centers, including spiro heterocyclic molecules. The dominant method in enantioselective synthesis based on synergistic includes aminocatalysis and NHC catalysis, as already established covalent organocatalytic strategies. Another area widely combined TM producing enantiomerically enriched is non‐covalent dominated by phosphoric acids, thiourea, squaramide derivatives. This review article aims to summarize methods constructing spirocyclic heterocycles a catalysis.

Язык: Английский

Процитировано

16
Combined Power of Organo‐ and Transition Metal Catalysis in Organic Synthesis DOI
Nikita Chakraborty, Bubul Das, Kamal Krishna Rajbongshi

и другие.

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(20)

Опубликована: Апрель 22, 2022

Abstract The combination of organocatalysis with transition metal catalysis is an emerging research area for the scientific community. Various unprecedented transformations that are otherwise inaccessible by individual catalytic systems can be achieved good efficiency and stereocontrolled manner this dual‐catalytic strategy. This Review presents a detailed discussion on recent advances in dual combining catalysis, covering literature last five years. A wide variety combinations metals organocatalysts including aminocatalysts, such as secondary amines more primary amines, Brønsted acid catalysts, especially phosphoric acids based chiral BINOL scaffold N ‐heterocyclic carbene discussed. Considering great contribution domain to organic synthesis, present future potential new exciting field highlighted.

Язык: Английский

Процитировано

21
Kinetic and Dynamic Kinetic Resolution by Dual Catalysis DOI

Gangavara L. Thejashree,

Eric Doris, Edmond Gravel

и другие.

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(44)

Опубликована: Окт. 18, 2022

Abstract Kinetic resolution is one of the most common methods to access enantiomerically enriched compounds. In this method, based on existing difference in reaction rates two enantiomers with a chiral catalyst. dynamic kinetic resolution, less reactive enantiomer racemized and racemic mixture further resolved, leading eventually complete transformation an enantioenriched compound. This review summarizes dual catalytic strategies ( i. e ., modular combinations distinct catalysts) that have been applied resolution. We focus upon role catalysts, compatibility between them, practical benefits.

Язык: Английский

Процитировано

13
Dynamic Kinetic Asymmetric Transformation of Racemic Diastereomers: Diastereo‐ and Enantioconvergent Michael–Henry Reactions to Afford Spirooxindoles Bearing Furan‐Fused Rings DOI
Muhammad Sohail, Fujie Tanaka

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(39), С. 21256 - 21260

Опубликована: Июль 8, 2021

Dynamic kinetic asymmetric transformation (DYKAT) reactions of racemic diastereomer mixtures that afford the products as essentially single diastereomers with high enantioselectivities are described. We demonstrated DYKAT in diastereo- and enantioselective synthesis spirooxindoles bearing furan-fused rings. The starting materials DYKAT, dihydrobenzofuranone derivatives, were synthesized mixtures, these transformed to spirooxindole derivatives yields through Michael-Henry cascade nitrostyrenes under organocatalytic conditions. In reactions, regardless stereochemistry materials, all four isomers enantioselectivities, new chiral centers created.

Язык: Английский

Процитировано

18
Remote Enantioselective ε‐Alkylation of Copper Ethynylallenylidenes: Precise Control of Central and Axial Chirality DOI

Yu‐Hua Wen,

Minghao Liu, Yuhao Wang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Окт. 17, 2024

Chiral tetrasubstituted allenes have emerged as important architectures for engineering biologically active compounds. The construction of unique allene scaffolds with precise control continuous central and axial chirality remains yet to be developed. Here, we report a remote enantioselective ϵ-alkylation yne-propargylic acetates enals enabled by NHC copper cooperative catalysis, leading series excellent enantioselectivities (up >99 % ee) diastereoselectivities >95 : 5 dr). This method features high regioselectivity simultaneous chirality. Mechanistic studies suggest activation mode synergistic distal created from the ethynylallenylidenes.

Язык: Английский

Процитировано

2
Enantioselective Dual Catalysis of N‐Heterocyclic Carbene and Hydrogen‐Bond Donor Organocatalysts DOI
Hongling Wang, Yonggui Robin, Xuan Huang

и другие.

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(27)

Опубликована: Июнь 21, 2022

Abstract N ‐heterocyclic carbene (NHC) catalysis has become a versatile strategy for building molecules via unique reaction modes. Dual catalytic processes using NHCs in combination with additional modulating agents such as another organocatalyst or transition‐metal catalyst have also been studied. The clear selection of cocatalysts led to enhanced reactivity, increased yields, and/or improved stereoselectivity. This minireview is provide readers brief overview the development and applications NHC hydrogen‐bond donor dual reactions.

Язык: Английский

Процитировано

10
A Simple and Fast Access to Phosphine‐Substituted Copper(I)‐Carbene Complexes via C=Se Bond Cleavage Reaction DOI

Sabari Veerapathiran,

Ganesan Prabusankar

Chemistry - An Asian Journal, Год журнала: 2023, Номер 18(11)

Опубликована: Апрель 17, 2023

Phosphine coordinated copper(I)-N-heterocyclic carbene complexes have emerged as an efficient material in catalysis and light-emitting applications. In this study, a gentle sustainable approach to the copper(I)-carbene phosphine is reported through C=Se activation protocol. The [(Py^NHC)Cu(PPh3 )2 ]X, X=BF4 (1), ClO4 (2), PF6 (3) OTf (4); Py^NHC=3-isopropyl-1-(pyridin-2-yl)-imidazol-2-ylidene, )(X)], X=Br (5) I (6) been synthesized by treating 1-isopropyl-3-(pyridin-2-yl)-imidazole-2-selone with corresponding copper(I) precursors triphenylphosphine. synthetic strategy, N-heterocyclic gets transferred from selone bond cleavage reaction form within five minutes at room temperature. addition, mechanism responsible for has fully investigated. These reactions are not sensitive moisture oxygen.

Язык: Английский

Процитировано

4
Asymmetric Redox Allylic Alkylation to Access 3,3′‐Disubstituted Oxindoles Enabled by Ni/NHC Cooperative Catalysis DOI Open Access

Tao Fan,

Jin Song, Liu‐Zhu Gong

и другие.

Angewandte Chemie, Год журнала: 2022, Номер 134(22)

Опубликована: Март 3, 2022

Abstract The feasibility of cooperative catalysis between chiral N‐heterocyclic carbenes and nickel in asymmetric reactions has been demonstrated convincingly. high efficiency this catalytic system enables the allylic alkylation isatin‐derived enals with carbonates [3+3] annulation racemic vinyl epoxides to provide straightforward access highly enantioenriched 3,3’‐disubstituted oxindoles. great practicality method organic synthesis showcased by facile product modification enantioselective key building block (−)‐debromoflustramine B.

Язык: Английский

Процитировано

5