Ligand-Controlled Copper(I)-Catalyzed Cross-Coupling of Secondary and Primary Alcohols to α-Alkylated Ketones, Pyridines, and Quinolines

Da-Wei Tan^†,Hong-Xi Li^*†‡（李红喜）,Da-Liang Zhu^†,Hai-Yan Li^†,David James Young^§,Jian-Lin Yao^*†（姚建林）, andJian-Ping Lang^*†‡（郎建平）

^†College of Chemistry, Chemical Engineering and Materials Science,Soochow University, Suzhou 215123,China

^‡State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences, Shanghai 200032,China

^§Faculty of Science, Health, Education and Engineering,University of the Sunshine Coast, Maroochydore DC, Queensland 4558,Australia

Org. Lett.,2018,20(3), 608--611

One hexanuclear Cu(I) cluster of 4,6-dimethylpyrimidine-2-thiolate efficiently catalyzes the dehydrogenative cross-coupling of secondary and primary alcohols to α-alkylated ketones with high selectivity. This transformation proceeds through a one-pot sequence of dehydrogenation of alcohols, condensation of aldehydes and ketones, hydrogenation of the resulting α,β-unsaturated ketones, and dehydrogenation of the α-alkylated alcohols to generate α-alkylated ketones. This catalytic system also displays high activity for the annulation reaction of secondary alcohols with γ-amino- and 2-aminobenzyl alcohols to yield pyridines and quinolines, respectively.

链接：https://pubs.acs.org/doi/10.1021/acs.orglett.7b03726