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硼酸盐配合物在亲电试剂诱导下的立体专一 1,2-迁移。

Stereospecific 1,2-Migrations of Boronate Complexes Induced by Electrophiles.

机构信息

School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.

出版信息

Angew Chem Int Ed Engl. 2020 Sep 21;59(39):16859-16872. doi: 10.1002/anie.202008096. Epub 2020 Jul 22.

DOI:10.1002/anie.202008096
PMID:32592274
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7540471/
Abstract

The stereospecific 1,2-migration of boronate complexes is one of the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals to natural products. Typically, 1,2-migration of boronate complexes is driven by displacement of an α-leaving group, oxidation of an α-boryl radical, or electrophilic activation of an alkenyl boronate complex. The aim of this article is to summarize the recent advances in the rapidly expanding field of electrophile-induced stereospecific 1,2-migration of groups from boron to sp and sp carbon centers. It will be shown that three different conceptual approaches can be utilized to enable the 1,2-migration of boronate complexes: stereospecific Zweifel-type reactions, catalytic conjunctive coupling reactions, and transition metal-free sp -sp couplings. A discussion of the reaction scope, mechanistic insights, and synthetic applications of the work described is also presented.

摘要

硼化合物的立体专一 1,2-迁移是硼化学中最具代表性的反应之一。该过程已被广泛用于开发强大的不对称合成方法，应用范围从药物到天然产物。通常，硼酸盐配合物的 1,2-迁移是由α-离去基团的取代、α-硼自由基的氧化或烯基硼酸盐配合物的亲电活化驱动的。本文的目的是总结在快速发展的领域中，从硼到 sp 和 sp 碳原子的立体专一性基团的电诱导 1,2-迁移的最新进展。将表明，可以利用三种不同的概念方法来实现硼酸盐配合物的 1,2-迁移：立体专一性 Zweifel 型反应、催化共轭偶联反应和无过渡金属的 sp-sp 偶联。还介绍了所描述工作的反应范围、机理见解和合成应用的讨论。

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2
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9
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6
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7
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8
Reactions of organoboron compounds enabled by catalyst-promoted metalate shifts.由催化剂促进的金属酸盐迁移实现的有机硼化合物反应。
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9
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Angew Chem Int Ed Engl. 2019 May 13;58(20):6654-6658. doi: 10.1002/anie.201901927. Epub 2019 Apr 4.
10
Carbopalladation of C-C σ-bonds enabled by strained boronate complexes.受张力硼酸酯配合物激活的 C-C σ 键碳钯化反应。
Nat Chem. 2019 Feb;11(2):117-122. doi: 10.1038/s41557-018-0181-x. Epub 2018 Dec 10.