Differential Dihydrofunctionalization: A Dual Catalytic Three-Component Coupling of Alkynes, Alkenyl Bromides, and Pinacolborane

被引：8

作者：

Baumann, James E. ^{[1
]}

Lalic, Gojko ^{[1
]}

机构：

[1] Univ Washington, Dept Chem, Seattle, WA 98195 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 37期

关键词：

Alkynes; Boron; Copper; Homogeneous Catalysis; Palladium; ANTI-MARKOVNIKOV HYDRATION; TERMINAL ALKYNES; INTRAMOLECULAR HYDROALKOXYLATION; REDUCTIVE HYDRATION; COMPLEXES; HYDROAMINATION; HYDROBORATION; ALDEHYDES; LIGAND; CONVERSION;

D O I：

10.1002/anie.202206462

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A new method for differential dihydrofunctionalization of terminal alkynes enables the synthesis of allylic boronate esters through reductive three-component coupling of terminal alkynes, alkenyl bromides, and pinacolborane. The transformation is promoted by cooperative action of a copper/palladium catalyst system and results in hydrofunctionalization of both pi-bonds of an alkyne. The synthesis of allylic boronate esters can be accomplished in the presence of a wide range of functional groups, including, esters, nitriles, alkyl halides, sulfonyl esters, acetals, protected terminal alkynes, aryl halides, and silyl ethers. Mechanistic experiments reveal the importance of subtle ligand effects on the performance of the palladium co-catalyst.

引用

页数：6

共 69 条

[1] Application of the Lithiation-Borylation Reaction to the Preparation of Enantioenriched Allylic Boron Reagents and Subsequent In Situ Conversion into 1,2,4-Trisubstituted Homoallylic Alcohols with Complete Control over All Elements of Stereochemistry [J].