A Homolytic Substitution Approach for Directing Group-Free Nickel-Catalyzed Dialkylation of Unactivated Alkenes

被引：0

作者：

Cong, Fei ^{[1
]}

Ng, Jun Wei ^{[1
]}

Koh, Ming Joo ^{[1
]}

机构：

[1] Natl Univ Singapore, Dept Chem, 4 Sci Dr 2, Singapore 117544, Singapore

来源：

SYNLETT | 2025年 / 36卷 / 03期

关键词：

nickel catalysis; dialkylation; unactivated alkenes; bimolecular homolytic substitution; radicals; REDOX-ACTIVE ESTERS; COUPLING REACTIONS; DIFUNCTIONALIZATION; DICARBOFUNCTIONALIZATION; ARYLATION; STYRENES; ACIDS;

D O I：

10.1055/a-2352-4902

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The selective construction of two C(sp(3))-C(sp(3)) 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 beta-hydride elimination or protodemetalation. Recently, our group was successful in developing a bimolecular homolytic substitution (S(H)2) 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

引用

页码：199 / 205

页数：7

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