Open AccessDirecting-group-free catalytic dicarbofunctionalization of unactivated alkenes
Author(s) -
Hongyu Wang,
Chen-Fei Liu,
R. Torrence Martin,
Osvaldo Gutiérrez,
Ming Joo Koh
Publication year - 2021
Publication title -
nature chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 9.996
H-Index - 232
eISSN - 1755-4349
pISSN - 1755-4330
DOI - 10.1038/s41557-021-00836-6
Subject(s) - chemistry , regioselectivity , alkene , nucleophile , aryl , reagent , catalysis , combinatorial chemistry , yield (engineering) , organic synthesis , organic chemistry , functional group , adduct , alkyl , materials science , metallurgy , polymer
In the absence of directing auxiliaries, the catalytic addition of carbogenic groups to unactivated alkenes with control of regioselectivity remains an ongoing challenge in organic chemistry. Here we describe a directing-group-free, nickel-catalysed strategy that couples a broad array of unactivated and activated olefins with aryl-substituted triflates and organometallic nucleophiles to afford diarylation adducts in either regioisomeric form, in up to 93% yield and >98% site selectivity. By switching the reagents involved, the present strategy may be extended to other classes of dicarbofunctionalization reactions. Mechanistic and computational investigations offer insights into the origin of the observed regiochemical outcome and the utility of the method is highlighted through the concise syntheses of biologically active molecules. The catalyst control principles reported are expected to advance efforts towards the development of general site-selective alkene functionalizations, removing the requirement for neighbouring activating groups.