Efficient Access to Enantioenriched gem-Difluorinated Heterocycles via Silver-Catalyzed Asymmetric Cycloaddition Reaction

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2024-04-24 DOI:10.1021/acscatal.4c01805

Jun Liu, Lijun Xu, Xiaolong Yu, Meijuan Zhou*, Hongyu Wang* and Gang Zhao*,

引用次数: 0

Abstract

gem-Difluorinated alkenes represent versatile building blocks to divergently access functional molecules containing gem-difluorinated methyl groups; however, little advances have been made on the transformations of gem-difluoro-1,3-dienes, particularly for the enantioselective versions. In this paper, we introduced an enantioselective [4 + 2] cycloaddition of gem-difluoro-1,3-butadienes with azodicarbonates catalyzed by AgSF₆ and (S)-MOP at a low catalyst loading that enables the generation of enantioenriched hydropyridazine derivatives in high yields and enantioselectivities (up to 98% yield, 98% ee). Control experiments and DFT analysis revealed that the cycloaddition reactions probably undergo a cascade reaction pathway, and azodicarbonates are activated by the chiral silver-(S)-MOP complex to control the enantioselectivities of the reactions.

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通过银催化的不对称环化反应高效获取对映体的二氟化宝石杂环

gem-二氟化烯是多用途的构筑基块，可用于不同地获得含有gem-二氟化甲基的功能分子；然而，在gem-二氟-1,3-二烯的转化方面进展甚微，尤其是在对映体选择性方面。在本文中，我们介绍了在 AgSF6 和 (S)-MOP 催化下，以较低的催化剂装填量实现了宝石-二氟-1,3-丁二烯与偶氮二碳酸盐的对映体选择性[4 + 2]环加成，从而以较高的产率和对映体选择性（高达 98% 的产率和 98% 的ee）生成了对映体丰富的哒嗪衍生物。对照实验和 DFT 分析表明，环化反应可能经历了级联反应途径，偶氮二碳酸盐被手性银-(S)-MOP 复合物激活，从而控制了反应的对映选择性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.