jo7b02676_si_001.pdf (2.76 MB)
Switchable Chemoselective Transfer Hydrogenations of Unsaturated Carbonyls Using Copper(I) N‑Donor Thiolate Clusters
journal contribution
posted on 2018-01-09, 00:00 authored by Meng-Juan Zhang, Da-Wei Tan, Hong-Xi Li, David James Young, Hui-Fang Wang, Hai-Yan Li, Jian-Ping LangUnsaturated
alcohols and saturated carbonyls are important chemical,
pharmaceutical, and biochemical intermediates. We herein report an
efficient transfer hydrogenation protocol in which conversion of unsaturated
carbonyl compounds to either unsaturated alcohols or saturated carbonyls
was catalyzed by Cu(I) N-donor thiolate clusters along with changing
hydrogen source (isopropanol or butanol) and base (NaOH or K2CO3). Mechanistic studies supported by DFT transition
state modeling indicate that such a chemoselectivity can be explained
by the relative concentrations of Cu(I) monohydride and protonated
Cu(I) hydride complexes in each catalytic system.