Technical Institute of Fluorochemistry (TIF), Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, 30 South Puzhu Road, Nanjing, 211816, China.
Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania, 19104, USA.
Nat Commun. 2020 Nov 6;11(1):5638. doi: 10.1038/s41467-020-19194-x.
The catalytic generation of homoenolates and their higher homologues has been a long-standing challenge. Like the generation of transition metal enolates, which have been used to great affect in synthesis and medicinal chemistries, homoenolates and their higher homologues have much potential, albeit largely unrealized. Herein, a nickel-catalyzed generation of homoenolates, and their higher homologues, via decarbonylation of readily available cyclic anhydrides has been developed. The utility of nickel-bound homoenolates and their higher homologues is demonstrated by cross-coupling with unactivated alkyl bromides, generating a diverse array of aliphatic acids. A broad range of functional groups is tolerated. Preliminary mechanistic studies demonstrate that: (1) oxidative addition of anhydrides by the catalyst is faster than oxidative addition of alkyl bromides; (2) nickel bound metallocycles are involved in this transformation and (3) the catalyst undergoes a single electron transfer (SET) process with the alkyl bromide.
通过易获得的环状酸酐的脱羰反应，发展了镍催化的偕同醇盐及其更高同系物的生成。镍结合的偕同醇盐及其更高同系物的用途通过与未活化的烷基溴化物的交叉偶联得到了证明，生成了各种各样的脂肪族酸。广泛的官能团都可以被容忍。初步的机理研究表明：（1）催化剂中酸酐的氧化加成比烷基溴化物的氧化加成更快；（2）镍结合的金属环参与了这个转化过程；（3）催化剂与烷基溴化物发生单电子转移（SET）过程。
