1. Copper-Mediated Dehydrogenative C(sp3)–H Borylation of Alkanes
- Author
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Sang, Ruocheng, Han, Wangyujing, Zhang, Hanwen, Saunders, Carla M., Noble, Adam, and Aggarwal, Varinder K.
- Abstract
Borylations of inert carbon–hydrogen bonds are highly useful for transforming feedstock chemicals into versatile organoboron reagents. Catalysis of these reactions has historically relied on precious-metal complexes, which promote dehydrogenative borylations with diboron reagents under oxidant-free conditions. Recently, photoinduced radical-mediated borylations involving hydrogen atom transfer pathways have emerged as attractive alternatives because they provide complimentary regioselectivities and proceed under metal-free conditions. However, these net oxidative processes require stoichiometric oxidants and therefore cannot compete with the high atom economy of their precious-metal-catalyzed counterparts. Herein, we report that CuCl2catalyzes radical-mediated, dehydrogenative C(sp3)–H borylations of alkanes with bis(catecholato)diboron under oxidant-free conditions. This is a result of an unexpected dual role of the copper catalyst, which promotes oxidation of the diboron reagent to generate an electrophilic bis-boryloxide that acts as an effective borylating agent in subsequent redox-neutral photocatalytic C–H borylations.
- Published
- 2023
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