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Copper-Mediated Dehydrogenative C(sp 3 )-H Borylation of Alkanes.
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2023 Jul 19; Vol. 145 (28), pp. 15207-15217. Date of Electronic Publication: 2023 Jul 06. - Publication Year :
- 2023
-
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 CuCl <subscript>2</subscript> catalyzes radical-mediated, dehydrogenative C(sp <superscript>3</superscript> )-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.
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 145
- Issue :
- 28
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 37410056
- Full Text :
- https://doi.org/10.1021/jacs.3c02185