华中科技大学袁伟明团队报道了从酯通过光解辅助还原酰基交叉偶联(PARAC)策略获得酮。相关研究成果于2021年11月15日发表于国际顶尖学术期刊《德国应用化学》。
该文开发了一种镍/光氧双催化的两种不同羧酸酯的交叉亲电偶联反应,通过光氧辅助还原酰基交叉偶联(PARAC)策略合成酮。多种芳基,1o,2o,3o-烷基2吡啶酯可作为酰基亲电试剂,而N(酰氧基)邻苯二甲酰亚胺(NHPI酯)可作为1o,2o,3o-自由基前体。
PARAC策略提供了一种在温和和高度统一的条件下合成各种空间拥挤的3o-3o、3o-2o和芳基L3o酮的替代和可靠的方法,否则很难获得这些酮。综合实验和计算研究确定了酮形成的Ni(0)/Ni(I)/Ni(III)途径。
附:英文原文
Title: From Esters to Ketones via a Photoredox-Assisted Reductive Acyl Cross-Coupling (PARAC) Strategy
Author: Weiming Yuan, Xiaoxiang Xi, Yixin Luo, Weirong Li, Minghao Xu, Hongping Zhao, Yukun Chen, Songlin Zheng, Xiaotian Qi
Issue&Volume: 2021-11-15
Abstract: A nickel/photoredox dual-catalyzed cross-electrophile coupling of two different carboxylic acid esters towards the synthesis of ketones via a photoredox-assisted reductive acyl cross-coupling (PARAC) strategy is developed. A variety of aryl, 1 o , 2 o , 3 o -alkyl 2pyridyl esters can act as acyl electrophiles while N (acyloxy)phthalimides (NHPI esters) act as 1 o , 2 o , 3 o -radical precursors. Our PARAC strategy provides an alternative and reliable way to synthesize various sterically congested 3 o -3 o , 3 o -2 o , and aryl3 o ketones under mild and highly unified conditions, which have been otherwise difficult to access. The combined experimental and computational studies identified a Ni(0)/Ni(I)/Ni(III) pathway for ketone formation.
DOI: 10.1002/anie.202114731
Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202114731
Angewandte Chemie:《德国应用化学》,创刊于1887年。隶属于德国化学会,最新IF:12.959
官方网址:https://onlinelibrary.wiley.com/journal/15213773
投稿链接:https://www.editorialmanager.com/anie/default.aspx