Pd-Catalyzed Organometallic-Free Homologation of Arylboronic Acids Enabled by Chemoselective Transmetalation

被引：7
|
作者：
Bastick, Kane A. C. [1 ]
Watson, Allan J. B. [1 ]
机构：
[1] Univ St Andrews, Sch Chem, EaStCHEM, St Andrews KY16 9ST, Fife, Scotland
来源：
ACS CATALYSIS | 2023年 / 13卷 / 10期
基金：
英国工程与自然科学研究理事会;
关键词：
boron; catalysis; chemoselectivity; cross-coupling; homologation; palladium; BORONIC ESTERS; HECK REACTION; BORYLATION; ARYL; PROTODEBORONATION; HALIDES; VINYL;
D O I：
10.1021/acscatal.3c00921
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (Bpin) undergo a remarkably facile, yet rare, oxidative addition enabled by an alpha-boryl effect. Simultaneous chemoselective transmetalation allows use of these metalloid reagents for formal C1 insertion to deliver benzyl Bpin products without the requirement for stoichiometric organometallic reagents. The utility of the process is demonstrated by stepwise C(sp3)-C(sp2) cross-coupling of the boronic ester products into diarylmethane pharmacophores and electrophile/ nucleophile chemoselective cross-coupling. Control experiments that demonstrate the reactivity enhancement provided by the alpha- boryl effect are provided, along with a description of the limitations of the formal homologation process.
引用
收藏
页码：7013 / 7018
页数：6
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