Dicarbofunctionalizations of an Unactivated Alkene via Photoredox/Nickel Dual Catalysis

Abstract

1,2-Dicarbofunctionalization of unactivated olefin has been reported under photoredox/nickel dual catalysis. The mildness of the visible-light-mediated reaction allows the use of various alkyl and aryl electrophiles with several sensitive functional groups. The protocol was equally applied for late-stage diversification of drugs and biologically active molecules. Investigations elucidated the importance of photoredox/nickel dual catalysis and α-amino-radical-mediated halogen atom transfer and provided us with the nickel complexes involved in the reaction.

A free-radical design featuring an intramolecular migration for a synthetically versatile alkyl–(hetero)arylation of simple olefins

“…Transition-metalcatalyzed conjunctive couplings between an olen, an aromatic partner, and an aliphatic partner have received the most attention to this end. [35][36][37][38][39][40][41][42][43][44][45][46][47] Productive olens, however, have overwhelmingly required either an activating group (conjugated p-bond or heteroatom) or a Lewis basic directing group (Fig. 1a, bottom) to promote olen-catalyst binding, which restricts the alkenes that can be valorized and the products that can be obtained.…”

Copper-catalyzed Markovnikov hydroboration of aliphatic terminal alkenes using carbonyl as a weak directing group

“…1 Although significant progress has been made, the reported methods generally show anti-Markovnikov regioselectivity. 2 The exploration of Markovnikov selective hydrofunctionalization of unactivated alkenes is still underdeveloped (Scheme 1a). 3 Only a few Markovnikov hydrocarbofunctionalizations or hydroaminations of unactivated CC bonds using 8-aminoquinoline (AQ) or amides as directing groups are disclosed so far, which generally utilized metal hydrides as the catalyst in combination with electrophilic reagents.…”