Terminal C(sp ³ )–H borylation through intermolecular radical sampling

Abstract

Hydrogen atom transfer (HAT) processes can overcome the strong bond dissociation energies (BDEs) of inert C(sp 3 )–H bonds and thereby convert feedstock alkanes into value-added fine chemicals. Nevertheless, the high reactivity of HAT reagents, coupled with the small differences among various C(sp 3 )–H bond strengths, renders site-selective transformations of straight-chain alkanes a great challenge. Here, we present a photocatalytic intermolecular radical sampling process for the iron-catalyzed borylation of terminal C(sp 3 )–H bonds in substrates with small steric hindrance, including unbranched alkanes. Mechanistic investigations have revealed that the reaction proceeds through a reversible HAT process, followed by a selective borylation of carbon radicals. A boron-sulfoxide complex may contribute to the high terminal regioselectivity observed.

Terminal-selective C(sp3)–H borylation of unbranched alkanes enabled by intermolecular radical sampling and LMCT photocatalysis

“…described a terminal-selective C(sp 3 )–H borylation of unbranched alkanes enabled by the ‘intermolecular radical sampling’ process (Fig. 1B ) [ 7 ]. Using iron photocatalysis, chlorine radicals are generated through homolysis and exploited as a HAT reagent, generating a series of alkyl radicals through unselective HAT.…”