具有可调手性口袋的SPSiBox使cu催化的对映选择性碳烯插入Ge-H和Si-H键

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Shi-Hao Chen, Shengye Zhang, Zi-Yang Chen, Yichen Wu, Peng Wang
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引用次数: 0

摘要

在这里,我们报道了cu催化的不对称碳插入到α-三氟甲基重氮化合物的Ge-H和Si-H键上,这是由一类新开发的c2对称双恶唑啉配体实现的。该方案具有底物范围广、反应条件温和、对映选择性好、催化剂负载低等特点,为制备富集对映体的α-三氟甲基石榴烷和有机硅烷提供了一种高效的方法。Si-H和Ge-H键的耐受性的关键是SPSiBox配体具有柔性和可调的手性口袋。初步的机制研究和计算研究揭示了SPSiBox配体手性诱导的起源,cu催化Ge-H插入的机制。该方法不仅为构建含三氟甲基的手性分子提供了新方法,而且为手性含硅、含锗功能分子的制备开辟了新途径。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Cu-Catalyzed Enantioselective Carbene Insertion into Ge–H and Si–H Bonds Enabled by SPSiBox with a Tunable Chiral Pocket

Cu-Catalyzed Enantioselective Carbene Insertion into Ge–H and Si–H Bonds Enabled by SPSiBox with a Tunable Chiral Pocket
Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge–H and Si–H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed C2-symmetrical bisoxazoline ligands. This protocol provides an efficient method for the preparation of enantioenriched α-trifluoromethyl ogranogermanes and organosilanes, featuring a broad substrate scope, mild reaction conditions, excellent enantioselectivity, and low catalyst loading. The key to the tolerance of both Si–H and Ge–H bonds is the use of SPSiBox ligands bearing a flexible and tunable chiral pocket. Preliminary mechanistic studies and computational studies unveiled the origin of chiral induction with SPSiBox ligands, the mechanism of Cu-catalyzed Ge–H insertion. This method not only provides a new method for the construction of trifluoromethyl-containing chiral molecules but also opens a new avenue for the preparation of chiral Si- and Ge-containing functional molecules.
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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