钯催化仲醇碳-氧交叉偶联的改进方法
Improved Process for the Palladium-Catalyzed C-O Cross-Coupling of Secondary Alcohols.
作者信息
Zhang Hong, Ruiz-Castillo Paula, Schuppe Alexander W, Buchwald Stephen L
机构信息
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
出版信息
Org Lett. 2020 Jul 17;22(14):5369-5374. doi: 10.1021/acs.orglett.0c01668. Epub 2020 Jun 24.
Abstract
An improved protocol for the Pd-catalyzed C-O cross-coupling of secondary alcohols is described. The use of biaryl phosphine as the ligand was key to achieving efficient cross-coupling of (hetero)aryl chlorides with only a 20% molar excess of the alcohol. Additionally, we observed an unusual reactivity difference between an electron-rich aryl bromide and the analogous aryl chloride, and deuterium-labeling suggested that currently unidentified pathways for reduction play an important role in explaining this disparity.
摘要
描述了一种改进的钯催化仲醇碳-氧交叉偶联反应方案。使用联芳基膦作为配体是实现（杂）芳基氯化物与仅20%摩尔过量醇高效交叉偶联的关键。此外，我们观察到富电子芳基溴化物与类似芳基氯化物之间存在异常的反应活性差异，氘标记表明目前尚未确定的还原途径在解释这种差异中起重要作用。
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