Open AccessA site-selective amination catalyst discriminates between nearly identical C–H bonds of unsymmetrical disubstituted alkenes
Author(s) -
Honghui Lei,
Tomislav Rovis
Publication year - 2020
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/s41557-020-0470-z
Subject(s) - chemistry , regioselectivity , amination , allylic rearrangement , steric effects , catalysis , stereochemistry , coupling reaction , combinatorial chemistry , medicinal chemistry , organic chemistry
C-H activation reactions enable chemists to unveil new retrosynthetic disconnections and streamline conventional synthetic approaches. A long-standing challenge in C-H activation is the inability to distinguish electronically and sterically similar C-H bonds. Although numerous synergistic combinations of transition-metal complexes and chelating directing groups have been utilized to distinguish C-H bonds, undirected regioselective C-H functionalization strategies remain elusive. Here we report a regioselective C-H activation/amination reaction of various unsymmetrical dialkyl-substituted alkenes. The regioselectivity of C-H activation is correlated to the electronic properties of allylic C-H bonds indicated by the corresponding 1 J CH coupling constants. A linear relationship between the difference in the 1 J CH coupling constants of the two competing allylic C-H bonds (Δ 1 J CH ) and the C-H activation barriers (ΔΔG ‡ ) has also been determined.