Redox-Neutral Ni-Catalyzed sp³ C–H Alkylation of α-Olefins with Unactivated Alkyl Bromides

Abstract

A light-induced redox-neutral Ni-catalyzed sp3 C–H alkylation of unactivated alkenes with alkyl bromides possessing β-hydrogens is described herein. The method is distinguished by its simplicity, wide scope, and exquisite regio- and chemoselectivity profile, thus offering an entry point to forge sp3–sp3 architectures.

Nickel‐Catalyzed Site‐Selective Intermolecular C(sp3)−H Amidation

“…Specifically, we hypothesized that we could harness the inherent electrophilicity of in situ generated Ni-nitrenoids II to enable a polarity-match, siteselective hydrogen-atom transfer (HAT) at hydridic C-(sp 3 )À H sites, [14c, 19] thus setting the basis for forging the targeted C(sp 3 )À N linkage via reductive elimination from in situ generated V while regenerating the active propagating Ni I species (Scheme 2). As part of our ongoing interest in Ni-catalyzed C(sp 3 )À H functionalization, [20] we describe herein the successful realization of this goal, culminating in the development of a broadly applicable, yet site-selective, protocol for incorporating amine functions at sp 3 sites.…”

α‐Amino Radical Halogen Atom Transfer Agents for Metallaphotoredox‐Catalyzed Cross‐Electrophile Couplings of Distinct Organic Halides

“…As demonstrated herein by the broad scope of applications in late-stage functionalization, this method represents an attractive tool for synthetic and medicinal chemists to rapidly build molecular complexity and contributes to a rapidly developing field of XAT dual first-row transition metal catalysis. [11,12,22,23] Future challenges include expanding the scope of organic halide partners to aryl/alkyl chlorides without bulky silane XAT agents.…”

“…A particularly attractive feature of the method is it can deliver products in high yields when employing either coupling partner as the limiting reactant, allowing user‐flexibility to accommodate and limit the organic halide partner with greatest cost or pharmaceutical importance. As demonstrated herein by the broad scope of applications in late‐stage functionalization, this method represents an attractive tool for synthetic and medicinal chemists to rapidly build molecular complexity and contributes to a rapidly developing field of XAT dual first‐row transition metal catalysis [11,12,22,23] . Future challenges include expanding the scope of organic halide partners to aryl/alkyl chlorides without bulky silane XAT agents.…”

The recent advances in cobalt-catalyzed C(sp3)–H functionalization reactions

“…Hence, there is an apparent need to explore and develop alternative catalysts that provide acceptable yields under feasible reaction conditions. The 1 st -row transition metal-based catalysts like manganese, 4 iron, 5 cobalt, 6 nickel, 7 and copper 8 are attracting the attention of several organic chemists due to their appealing properties like high abundance, low cost, and low toxicity. As every catalytic system is fundamentally different, not every transition metal-based catalyst can furnish the desired results.…”