Improvement in the Palladium-Catalyzed Miyaura Borylation Reaction by Optimization of the Base: Scope and Mechanistic Study

被引：40

作者：

Barroso, Santiago ^{[1
]}

Joksch, Markus ^{[2
]}

Puylaert, Pim ^{[2
]}

Tin, Sergey ^{[2
]}

Bell, Stephen J. ^{[3
]}

Donnellan, Luke ^{[3
]}

Duguid, Stewart ^{[3
]}

Muir, Colin ^{[3
]}

Zhao, Peichao ^{[3
]}

Farina, Vittorio ^{[4
]}

Tran, Duc N. ^{[1
]}

de Vries, Johannes G. ^{[2
]}

机构：

[1] Janssen Pharmaceut, Dept API SM Dev, B-2340 Beerse, Belgium

[2] Univ Rostock, Leibniz Inst Katalyse Ev, D-18059 Rostock, Germany

[3] Almac Sci, Dept Proc Dev, Craigavon BT63 5QD, North Ireland

[4] Farinachem Consulting GmbH, D-52072 Aachen, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2021年 / 86卷 / 01期

关键词：

CROSS-COUPLING REACTION; ARYL HALIDES; COMPLEXES; CHLORIDES; BROMIDES; ROUTE;

D O I：

10.1021/acs.joc.0c01758

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Aryl boronic acids and esters are important building blocks in API synthesis. The palladium-catalyzed Suzuki-Miyaura borylation is the most common method for their preparation. This paper describes an improvement of the current reaction conditions. By using lipophilic bases such as potassium 2-ethyl hexanoate, the borylation reaction could be achieved at 35 degrees C in less than 2 h with very low palladium loading (0.5 mol %). A preliminary mechanistic study shows a hitherto unrecognized inhibitory effect by the carboxylate anion on the catalytic cycle, whereas 2-ethyl hexanoate minimizes this inhibitory effect. This improved methodology enables borylation of a wide range of substrates under mild conditions.

引用

页码：103 / 109

页数：7

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