Ni-Catalyzed Ligand-Controlled Selective 5-Exo and 6-EndoCyclization/Cross-Couplings Involving an Unusual 1,2-Aryl Migration

被引：12

作者：

Yang, Miao ^{[1
]}

Liu, Ning ^{[1
]}

Zhang, Zhanhao ^{[1
]}

She, Yuan-Bin ^{[1
]}

Yang, Yun-Fang ^{[1
]}

机构：

[1] Zhejiang Univ Technol, Coll Chem Engn, Hangzhou 310014, Zhejiang, Peoples R China

来源：

ACS CATALYSIS | 2022年 / 12卷 / 07期

基金：

中国国家自然科学基金;

关键词：

1; 2-aryl migration; Ni catalysis; density functional theory; regiodivergence; cross-coupling; MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; BASIS-SETS; COUPLING REACTIONS; METHANE HYDROXYLATION; NICKEL; ARYL; DICARBOFUNCTIONALIZATION; CYCLIZATION; REACTIVITY;

D O I：

10.1021/acscatal.1c05466

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Nickel-catalyzed ligand-controlled reductive dicar-bofunctionalization of alkenes provides a regiodivergent syntheticstrategy for constructingfive- and six-membered benzo-fusedlactams bearing all-carbon quaternary centers. Density functionaltheory (DFT) calculations have been carried out to elucidate thedetailed mechanisms of this 5-exo vs 6-endo Heck cyclization/cross-coupling reaction. The computational results suggest that 5-exo is favored over 6-endo in the cyclization step with either thebidentate bipyridine ligand or the tridentate C6-carboxylic acid-modified bipyridine ligand. Multiple mechanistic pathwaysinvolving different Ni oxidation states might be operative for theformation of the 5-exo Heck cyclization/cross-coupling productwith the bidentate bipyridine ligand. By contrast, the tridentate C6-carboxylic acid-modified bipyridine ligand favors the NiIIIpathway, and the 5-exo cyclization NiIII-alkyl intermediate undergoes anunusual 1,2-aryl migration to form the 6-endo ring expansion cross-coupling product

引用

页码：4131 / 4140

页数：10