ic7b00226_si_001.pdf (1.18 MB)
Tripodal S‑Ligand Complexes of Copper(I) as Catalysts for Alkene Aziridination, Sulfide Sulfimidation, and C–H Amination
Version 2 2017-05-24, 12:22
Version 1 2017-03-30, 15:20
journal contribution
posted on 2017-04-17, 00:00 authored by Tsz Lung Lam, Ken Chi-Hang Tso, Bei Cao, Chen Yang, Daqing Chen, Xiao-Yong Chang, Jie-Sheng Huang, Chi-Ming CheCopper(I) complexes
of tris(thioimidazolyl)borates (R′TmR), including
[Cu(TmPh)(PR″3)] (R″ = Ph, Cu1; Cy, Cu2) and [Cu(R′TmPh)(PR″3)]+ (R′ = N-methylimidazole; R″ = Ph, Cy) were prepared and characterized
by spectroscopic methods. The X-ray crystal structures of Cu1 and Cu2 feature a tripodal TmPh ligand coordinated
in κ3-S,S,S mode. Using Cu2 as a catalyst
(loading: 1 mol %), the aziridination of styrenes and sulfimidation
of thioanisoles with PhINTs at RT for 3 and 0.5 h, respectively,
both resulted in product yields of up to 99%. Cu2 also
catalyzed intramolecular amination of the aryl C–H bond of
vinyl azides with up to 98% yield. DFT calculations were performed
to gain insight into the mechanism of the Cu2-catalyzed
aziridination reaction.