Metallaphotoredox Synthesis of Axially Chiral Tetrasubstituted Allenes through Regio- and Enantioselective 1,4-Carbocyanation of 1,3-Enynes

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2024-09-10 DOI:10.1021/acscatal.4c04330

Keyi Peng, Ya-Sheng Cao, Quanyuan Wang, Ziwei Xia, Ya Chen, Yixin Lu, Guo-Jun Deng

引用次数: 0

Abstract

Radical 1,4-difunctionalization of 1,3-enynes represents a promising approach for the rapid creation of allenes from readily available feedstocks. However, the enantioselective synthesis of tetra-substituted chiral allenes from 1,3-enynes via a radical pathway remains difficult. Herein, we disclose an enantioselective decarboxylative 1,4-carbocyanation of 1,3-enynes through photoredox and copper dual catalysis, affording a wide array of axially chiral tetra-substituted allenes in a highly chemoselective, regioselective, and enantioselective manner. This mild and redox-neutral protocol exhibits broad substrate scope and good functional group tolerance and enables late-stage allenyation of natural and drug-like molecules.

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通过 1,3-炔的 Regio- 和 Enantioselective 1,4-Carbocyanation 合成轴向手性四取代烯烃的 Metallaphotoredox 技术

1,3-烯炔的 1,4-自由基二官能化是利用现成原料快速制备烯烃的一种很有前景的方法。然而，通过自由基途径从 1,3-烯炔对映选择性地合成四取代手性烯烃仍然很困难。在此，我们公开了一种通过光氧化和铜双重催化对 1,3-enynes 进行对映体选择性脱羧的 1,4- 碳腈化反应，以高度化学选择性、区域选择性和对映体选择性的方式获得多种轴向手性四取代烯烃。这种温和且氧化还原中性的方案具有广泛的底物范围和良好的官能团耐受性，可用于天然分子和类药物分子的后期烯炔化。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.