Copper-Mediated Dehydrogenative C(sp3)-H Borylation of Alkanes

被引：41

作者：

Sang, Ruocheng ^{[1
]}

Han, Wangyujing ^{[1
]}

Zhang, Hanwen ^{[1
]}

Saunders, Carla M. ^{[1
]}

Noble, Adam ^{[1
]}

Aggarwal, Varinder K. ^{[1
]}

机构：

[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, England

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2023年 / 145卷 / 28期

基金：

英国工程与自然科学研究理事会;

关键词：

C-H BORYLATION; ALPHA; BETA-UNSATURATED CARBONYL-COMPOUNDS; IRIDIUM-CATALYZED BORYLATION; BONDS; FUNCTIONALIZATIONS; ACTIVATION; REACTIVITY; REDUCTION; SECONDARY; RADICALS;

D O I：

10.1021/jacs.3c02185

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Borylations of inertcarbon-hydrogen bonds arehighly usefulfor transforming feedstock chemicals into versatile organoboron reagents.Catalysis of these reactions has historically relied on precious-metalcomplexes, which promote dehydrogenative borylations with diboronreagents under oxidant-free conditions. Recently, photoinduced radical-mediatedborylations involving hydrogen atom transfer pathways have emergedas attractive alternatives because they provide complimentary regioselectivitiesand proceed under metal-free conditions. However, these net oxidativeprocesses require stoichiometric oxidants and therefore cannot competewith the high atom economy of their precious-metal-catalyzed counterparts.Herein, we report that CuCl2 catalyzes radical-mediated,dehydrogenative C(sp(3))-H borylations of alkaneswith bis(catecholato)diboron under oxidant-free conditions. This isa result of an unexpected dual role of the copper catalyst, whichpromotes oxidation of the diboron reagent to generate an electrophilicbis-boryloxide that acts as an effective borylating agent in subsequentredox-neutral photocatalytic C-H borylations.

引用

页码：15207 / 15217

页数：11

共 56 条

[1] Direct C-C Bond Formation from Alkanes Using Ni-Photoredox Catalysis [J].