引导无基团镍催化未活化烯烃二烷基化的均聚取代方法

IF 1.7 4区 化学 Q3 CHEMISTRY, ORGANIC Synlett Pub Date : 2024-07-15 DOI:10.1055/a-2352-4902
Fei Cong, Jun Wei Ng, Ming Joo Koh
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摘要

通过未活化烯烃的三分子交叉偶联选择性地构建两个 C(sp3)-C(sp3)键仍然是有机合成中最困难的挑战之一。尽管以前在金属催化偶联烯烃二官能化方面取得了进展,但由于必要的金属-烷基中间体不稳定,二烷基化仍然存在问题,因为它很容易发生β-酸酐消除或原脱醛反应。最近,我们的研究小组成功开发出一种双分子同溶取代(SH2)策略,这种策略可以避开金属-烷基副反应,在没有定向助剂的情况下完成金属-烷基中间体与烷基自由基的高难度交叉偶联,从而实现未活化烯烃的高区域选择性二烷基化。1 引言 2 镍催化未活化烯烃的二羧官能化 3 镍催化未活化烯烃的二烷基化 4 结论与展望
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A Homolytic Substitution Approach for Directing Group-Free Nickel-Catalyzed Dialkylation of Unactivated Alkenes

The selective construction of two C(sp3)–C(sp3) bonds through trimolecular cross-coupling of unactivated alkenes remains one of the most difficult challenges in organic synthesis. Despite previous advances in metal-catalyzed coupling for the dicarbofunctionalization of alkenes, dialkylation is still problematic due to the instability of the requisite metal–alkyl intermediate, which undergoes facile β-hydride elimination or protodemetalation. Recently, our group was successful in developing a bimolecular homolytic substitution (SH2) strategy that circumvents metal–alkyl side reactions and accomplishes the challenging cross-coupling of metal–alkyl intermediates with alkyl radicals in the absence of a directing auxiliary, permitting a highly regioselective dialkylation of unactivated alkenes.

1 Introduction

2 Nickel-Catalyzed Dicarbofunctionalization of Unactivated Alkenes

3 Nickel-Catalyzed Dialkylation of Unactivated Alkenes

4 Conclusions and Perspectives

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来源期刊
Synlett
Synlett 化学-有机化学
CiteScore
3.40
自引率
5.00%
发文量
369
审稿时长
1 months
期刊介绍: SYNLETT is an international journal reporting research results and current trends in chemical synthesis in short personalized reviews and preliminary communications. It covers all fields of scientific endeavor that involve organic synthesis, including catalysis, organometallic, medicinal, biological, and photochemistry, but also related disciplines and offers the possibility to publish scientific primary data.
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