Rhodium-Catalyzed Asymmetric Allylic Dearomatization of β-Naphthols with gem-Difluorinated Cyclopropanes

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2025-02-25 DOI:10.1021/acscatal.5c00315

Zi-Qi Yang, Yiliang Gong, Qing Gu, Shu-Li You

引用次数: 0

Abstract

Transition-metal-catalyzed allylation reactions using gem-difluorinated cyclopropanes have drawn considerable interest in recent years. However, linear-selective and enantioselective 2-fluoroallylic substitution reaction is underexplored. Herein, we report a rhodium-catalyzed asymmetric allylic dearomatization of β-naphthols with gem-difluorinated cyclopropanes. In the presence of a rhodium catalyst consisting of commercially available rhodium precursor and chiral bisphosphine ligand, linear-selective 2-fluoroallylic β-naphthalenones bearing quaternary carbon centers were obtained in good yields and enantioselectivity (up to 86% yield and 95% ee). Mechanistic studies disclosed that the NaBAr^F additive in this reaction is critical, and a kinetic resolution is operated for the C–C cleavage of the gem-difluorinated cyclopropane.

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铑催化β-萘酚与宝石二氟化环丙烷的不对称烯丙基脱芳化反应

近年来，使用宝石二氟化环丙烷的过渡金属催化烯丙化反应引起了相当大的兴趣。然而，线性选择性和对映选择性的2-氟烯丙基取代反应尚未得到充分的研究。本文报道了铑催化的β-萘酚与宝石二氟化环丙烷的不对称烯丙基脱芳反应。在由市售铑前体和手性双膦配体组成的铑催化剂的存在下，以良好的收率和对映选择性（高达86%的收率和95%的ee）获得了含季碳中心的2-氟烯基β-萘酮。机理研究表明，NaBArF添加剂在该反应中起着至关重要的作用，并对宝石二氟化环丙烷的C-C裂解进行了动力学解析。

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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.