Lithium Aryltrifluoroborate as a Catalyst for Halogen Transfer
Lithium Aryltrifluoroborate as a Catalyst for Halogen Transfer
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芳基三氟硼酸锂作为卤素转移催化剂
DOI：
10.1021/acscatal.2c06082
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发表时间：
2023
期刊：
影响因子：
12.9
通讯作者：
Okano Kentaro
中科院分区：
文献类型：
--
作者：
Inoue Kengo;Hirano Keiichi;Fujioka Shota;Uchiyama Masanobu;Mori Atsunori;Okano Kentaro
本文报道了芳基三氟硼酸锂对两个连续的溴-锂交换反应的催化作用。当负载量为10 mol %时，该催化剂表现出良好的溴代基团转移活性，并适用于各种溴代吡啶。密度泛函理论计算与所提出的机制一致，其中催化剂向单溴或二溴化底物提供溴原子，并且所得脱溴催化剂然后从二溴或三溴化底物中提取另一溴原子，导致底物上的溴基团的转座，催化剂再生。
The catalysis of two successive bromine–lithium exchange reactions, referred to as a “halogen dance”, by lithium aryltrifluoroborate is reported. At a loading of 10 mol %, this catalyst exhibited efficient activity for bromo group transfer and was applicable to various brominated pyridines. Density functional theory calculations were consistent with the proposed mechanism, where the catalyst provided a bromine atom to the mono- or dibrominated substrate and the resulting debrominated catalyst then abstracted another bromine atom from the di- or tribrominated substrate, leading to the transposition of the bromo group on the substrate with catalyst regeneration.