Experimental and Computational Studies on Cobalt(I)-Catalyzed Regioselective Allylic Alkylation Reactions

被引：5

作者：

Andreetta, Philip ^{[1
]}

Martin, Robert T. ^{[2
]}

Souilah, Charafa ^{[1
]}

Renteria-Gomez, Angel ^{[3
]}

Song, Zhihui ^{[2
]}

Bayat, Yas Khorramshahi ^{[1
]}

Ivlev, Sergei ^{[1
]}

Gutierrez, Osvaldo ^{[3
]}

Casitas, Alicia ^{[1
]}

机构：

[1] Philipps Univ Marburg, Fachbereich Chem, Hans Meerwein Str 4, D-35043 Marburg, Germany

[2] Univ Maryland, Dept Chem & Biochem, Coll Pk 8051 Regents Dr, College Pk, MD 20742 USA

[3] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 46期

基金：

美国国家卫生研究院;

关键词：

Allylic Alkylation Reaction; Cobalt Catalysis; Coordination Cobalt(I) Complexes; Reaction Mechanism; Theoretical Calculations; ENANTIOSELECTIVE SYNTHESIS; CATALYZED ALLYLATION; SYNTHETIC REACTIONS; CONJUGATE ADDITION; IRIDIUM COMPLEX; BITE ANGLE; COBALT; LIGAND; ARYL; SUBSTITUTION;

D O I：

10.1002/anie.202310129

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Here, we report the development of cobalt(I)-catalyzed regioselective allylic alkylation reactions of tertiary allyl carbonates with 1,3-dicarbonyl compounds. A family of well-defined tetrahedral cobalt(I) complexes bearing commercially available bidentate bis(phosphine) ligands [(P,P)Co(PPh3)Cl] are synthesized and explored as catalysts in allylic alkylation reactions. The catalyst [(dppp)Co(PPh3)Cl] (dppp=1,3-Bis(diphenylphosphino)propane) enables the alkylation of a large variety of tertiary allyl carbonates with high yields and excellent regioselectivity for the branched product. Remarkably, this methodology is selective for the activation of tertiary allyl carbonates even in the presence of secondary allyl carbonates. This contrasts with the selectivity observed in cobalt-catalyzed allylic alkylations enabled by visible light photocatalysis. Mechanistic insights by means of experimental and computational investigations support a Co(I)/Co(III) catalytic cycle.

引用

页数：8

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