Room-Temperature, Ligand- and Base-Free Heck Reactions of Aryl Diazonium Salts at Low Palladium Loading: Sustainable Preparation of Substituted Stilbene Derivatives

被引：84

作者：

Felpin, Francois-Xavier ^{[1
]}

Miqueu, Karinne ^{[2
]}

Sotiropoulos, Jean-Marc ^{[2
]}

Fouquet, Eric ^{[1
]}

Ibarguren, Oier ^{[1
]}

Laudien, Julia ^{[1
]}

机构：

[1] Univ Bordeaux, CNRS, ISM, UMR 5255, F-33405 Talence, France

[2] Univ Pau & Pays Adour, CNRS, IPREM, UMR 5254, F-64053 Pau 09, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 17期

关键词：

diazo compounds; density functional calculations; Heck reaction; palladium; sustainable chemistry; REDUCTION-CYCLIZATION HRC; CROSS-COUPLING REACTIONS; AB-INITIO PSEUDOPOTENTIALS; CATALYZED MIZOROKI-HECK; ARENEDIAZONIUM SALTS; ARYLDIAZONIUM SALTS; COMBRETASTATIN A-4; PALLADIUM(0)-CATALYZED ARYLATION; STEREOSELECTIVE-SYNTHESIS; ASYMMETRIC-SYNTHESIS;

D O I：

10.1002/chem.200903050

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The Pd(OAc)(2)-catalyzed Heck reaction of aryl diazonium salts with 2-arylacrylates led to cis-stilbenes with good to excellent stereoselectivity. The environmentally friendly protocol developed in this work features low palladium loading in technical-grade methanol at room temperature under base-, additive-, and ligand-free conditions. The same protocol applied to simple Heck coupling of aryl diazonium salts with methyl acrylate allows astonishingly low palladium loading, down to 0.005 mol %. The stereoselectivity experimentally observed for the synthesis of cis-stilbenes has been rationalized by DFT calculations. Moreover, the role of methanol in promoting the reaction has been clarified by a computational study.

引用

页码：5191 / 5204

页数：14