摘要：KEYWORDS:dechlorination,copper catalysis (反应类型), C(sp3)–H (成键类型), alkyl chloride (原料), C(sp3)–Cl (断键类型), DIBAL-H (其他), IPrCuCl(催化剂
转自：康龙化成
Cu-Catalyzed Hydrodechlorination of Unactivated Alkyl Chlorides Using Diisobutylaluminum Hydride
Subin Yoon,‡ Seeun Lim,‡ Soohong Cho,‡ and Yunmi Lee*
Department of Chemistry, Kwangwoon University, Seoul 01897, Republic of Korea
—Org. Lett. 2024, DOI: 10.1021/acs.orglett.4c03774
KEYWORDS: dechlorination,copper catalysis (反应类型), C(sp3)–H (成键类型), alkyl chloride (原料), C(sp3)–Cl (断键类型), DIBAL-H (其他), IPrCuCl(催化剂)
ABSTRACT: Acopper-catalyzed hydrodechlorination ofprimary, secondary, and tertiary alkyl chlorides using diisobutylaluminumhydride is reported. This catalytic system offers a broad substrate scope, highyields, and good functional group tolerance. Mechanistic investigationsindicated that the reaction predominantly proceeds via a radical pathway, assupported by radical clock experiments. Importantly, this study provides a newapproach for the selective hydrodechlorination of unactivated alkyl chlorides and expands the utility of Cuhydride catalysis in sustainable chemicalsynthesis.
Backgroundand This Work:
Proposed Mechanism
Prof. Yunmi Lee and his co-workers have described acopper-hydride-catalyzed method developed for the hydrodechlorination of primary,secondary, and tertiary alkyl chlorides using diisobutylaluminum hydride (DIBAL-H) asa hydride source. The optimized reaction conditions allowed the efficient andselective reduction of a broad range of substrates in high yields includingfunctionalized alkyl chlorides. Mechanistic studies strongly supported aradical pathway for these reactions, although an ionic mechanism cannot beruled out for certain substrates. Notably, these findings expand the scope of copperhydride catalysis by demonstrating its effectiveness in the hydrodechlorination of unactivated alkyl chlorides, which represent a challenging and generally underexploredsubstrate class. Future research will concentrate on exploring the use ofaluminum hydrides in various forms of CuH catalysis and focus on a more detailedinvestigation of the underlying mechanism to enhance understanding of theprocess.
来源：新浪财经
