高效实现 2-氮杂二烯的分子间羟烷氧基化和羟羧基化。
Intermolecular Hydroalkoxylation and Hydrocarboxylation of 2-Azadienes with High Efficiency.
机构信息
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
出版信息
J Org Chem. 2023 Mar 3;88(5):3277-3281. doi: 10.1021/acs.joc.2c02534. Epub 2023 Feb 21.
Abstract
Described here is a method for intermolecular hydroalkoxylation and hydrocarboxylation of 2-azadienes through cobalt-catalyzed hydrogen atom transfer and oxidation. This protocol provides a source of 2-azaallyl cation equivalents under mild conditions, is chemoselective in the presence of other C═C double bonds, and requires no excess amount of added alcohol or oxidant. Mechanistic studies suggest that the selectivity arises from lowering the transition state that leads to the highly stabilized 2-azaallyl radical.
摘要
这里描述了一种通过钴催化的氢原子转移和氧化实现 2-氮杂二烯的分子间氢烷氧基化和氢羧基化的方法。该方案在温和条件下提供了 2-氮烯丙基阳离子等价物的来源，在存在其他 C═C 双键的情况下具有化学选择性，并且不需要过量的添加醇或氧化剂。机理研究表明，选择性源于降低导致高度稳定的 2-氮烯丙基自由基的过渡态。
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