铑(I)催化的不对称烷基碳烯 B-H 键插入:多功能手性烷基硼烷的对映选择性合成

IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Jian-Guo Liu, Bo Liu, Ziyan Li, Ming-Hua Xu
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引用次数: 0

摘要

过渡金属-不对称碳烯 B-H 插入反应的最新进展为获得手性有机硼化合物提供了一个直接而强大的方案。然而,涉及线性烷基碳烯的相关反应尚未成功开发。除了难以控制对映选择性外,另一个主要挑战是烷基金属碳烯极易发生 β-酸酐迁移,形成不需要的烯烃。在此,我们报告了以铑(I)/二烯配合物为催化剂开发的高效烷基碳烯 B-H 插入反应。这种简单的催化体系不仅减少了烯烃副产物的生成,还实现了碳烯 B-H 插入反应的高对映选择性。这种方法可以方便地以高产率不对称地获得多种结构不同的烷基硼烷,并介绍了它们的进一步合成应用和转化。机理研究表明,在铑(I)/二烯催化体系下,β-酸酐迁移不如碳烯插入途径有利,B-H 键插入是限速步骤。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Rhodium(I)-Catalyzed Asymmetric Alkyl Carbene B–H Bond Insertion: Enantioselective Synthesis of Versatile Chiral Alkylboranes

Recent advances in transition metal-asymmetric carbene B–H insertion reactions provide a straightforward and powerful protocol to access chiral organoboron compounds. However, the related reaction involving linear alkyl carbenes has not been successfully developed. Apart from the difficulty of controlling the enantioselectivity, another major challenge is the high propensity of the alkyl metal carbene to undergo a β-hydride migration to form undesired alkenes. Herein, we report our development of an efficient alkyl carbene B–H insertion reaction using rhodium(I)/diene complexes as the catalysts. This simple catalytic system not only reduces the formation of alkene byproduct but also achieves high enantioselectivity of the carbene B–H insertion. This method facilitates easy asymmetric access to a wide variety of structurally diverse alkylboranes in high yields, and their further synthetic application and transformation have also been described. Mechanistic studies show that the β-hydride migration is less favorable than the carbene insertion pathway under the rhodium(I)/diene catalytic system and that the B–H bond insertion is the rate-limiting step.

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来源期刊
CCS Chemistry
CCS Chemistry Chemistry-General Chemistry
CiteScore
13.60
自引率
13.40%
发文量
475
审稿时长
10 weeks
期刊介绍: CCS Chemistry, the flagship publication of the Chinese Chemical Society, stands as a leading international chemistry journal based in China. With a commitment to global outreach in both contributions and readership, the journal operates on a fully Open Access model, eliminating subscription fees for contributing authors. Issued monthly, all articles are published online promptly upon reaching final publishable form. Additionally, authors have the option to expedite the posting process through Immediate Online Accepted Article posting, making a PDF of their accepted article available online upon journal acceptance.
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