Palladium-Catalyzed Allylic Alkylation of Simple Ketones with Allylic Alcohols and Its Mechanistic Study

被引：168

作者：

Huo, Xiaohong ^{[1
]}

Yang, Guoqiang ^{[2
]}

Liu, Delong ^{[1
]}

Liu, Yangang ^{[1
]}

Gridnev, Ilya D. ^{[3
]}

Zhang, Wanbin ^{[1
,2
]}

机构：

[1] Shanghai Jiao Tong Univ, Sch Pharm, 800 Dongchuan Rd, Shanghai 200240, Peoples R China

[2] Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Shanghai 200240, Peoples R China

[3] Tohoku Univ, Dept Chem, Grad Sch Sci, Aoba Ku, Sendai, Miyagi 9808578, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 26期

基金：

中国国家自然科学基金;

关键词：

allylic alcohol; allylic alkylation; DFT calculation; organocatalysis; palladium; ASYMMETRIC ALPHA-ALLYLATION; TRANSITION-METAL; SELECTIVE SYNTHESIS; COUPLING REACTION; DIRECT AMINATION; BOND-CLEAVAGE; LIGANDS; ALDEHYDES; PLATINUM; ACID;

D O I：

10.1002/anie.201403410

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Allylic alcohols were directly used in Pd-catalyzed allylic alkylations of simple ketones under mild reaction conditions. The reaction proceeded smoothly at 20 degrees C by the concerted action of a Pd catalyst, a pyrrolidine co-catalyst, and a hydrogen-bonding solvent, and does not require any additional reagents. A computational study suggested that methanol plays a crucial role in the formation of the pi-allylpalladium complex by lowering the activation barrier.

引用

页码：6776 / 6780

页数：5

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