Novel Sulfinamide-Based Chiral Ligand Promoted Chiral Diarylmethanol Preparation via exo-Directed Asymmetric C–H Alkynylation under Mild Conditions

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-01-28 DOI:10.1021/acscatal.4c0754910.1021/acscatal.4c07549

Xin Yu, Siqi Liu, Lei Wang, Ya Li, Meirong Huang, Zheng-Yang Yan, Hao-Chen Li, Qi Zhang*, Xinhao Zhang* and Bing-Feng Shi*,

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Abstract

Desymmetrization of diarylmethanols has been achieved by means of exo-directed Pd(II)-catalyzed C–H alkynylation under mild conditions (30 °C). We herein designed a class of chiral N-sulfinyl anthranilic acid (CSAA) ligands with chiral information only at the N-protecting group, which were found crucial for challenging stereocontrol within a conformationally flexible exo-chelated six-membered palladacycle. An array of valuable chiral diarylmethanols were obtained in high yield, good enantioselectivity, and broad functional group tolerance. Gram-scale synthesis was readily carried out and a diverse range of transformations were implemented with high retention of configuration, highlighting the synthetic utility of this method. Preliminary mechanistic studies indicated that CSAAs adopted an N,O-chelation mode, and the chiral induction proceeded through direct interaction between the N-tert-butanesulfinamide motif with the substrate.

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新型亚胺类手性配体在温和条件下外定向不对称C-H烷基化促进手性二芳基甲醇的制备

在温和条件下（30°C），通过外定向Pd（II）催化的C - h炔化反应实现了二芳基甲醇的脱对称。本文设计了一类仅在n保护基团上具有手性信息的n -亚硝基邻氨基苯甲酸（CSAA）配体，这类配体对于挑战构象柔性外螯合六元环的立体控制至关重要。以高收率、良好的对映选择性和广泛的官能团耐受性获得了一系列有价值的手性二芳基甲醇。克尺度的合成很容易进行，并且实现了各种各样的转换，具有很高的构型保留率，突出了该方法的合成实用性。初步机理研究表明，CSAAs采用N， o螯合模式，通过N-叔丁烷磺酰胺基序与底物的直接相互作用进行手性诱导。

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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.