Catalytic Cross-Coupling of Secondary Alcohols

Journal of the American Chemical Society
Subramanian Thiyagarajan, Chidambaram Gunanathan

Abstract

Herein, an unprecedented ruthenium(II) catalyzed direct cross-coupling of two different secondary alcohols to β-disubstituted ketones is reported. Cyclic, acylic, symmetrical, and unsymmetrical secondary alcohols are selectively coupled with aromatic benzylic secondary alcohols to provide ketone products. A single catalyst oxidizes both secondary alcohols to provide selectively β-disubstituted ketones to broaden the scope of this catalytic protocol. Number of bond activation and bond formation reactions occur in selective sequence via amine-amide metal-ligand cooperation operative in Ru-MACHO catalyst. The product-induced diastereoselectivity was also observed. Kinetic and deuterium labeling experiments suggested that the aliphatic secondary alcohols undergo oxidation reaction faster than benzylic secondary alcohols, selectively assimilating to provide the cross-coupled products. Reactions are sensitive to steric hindrance. This new C-C bond forming methodology requires low catalyst load and catalytic amount of base. Notably, the reaction produces H2 and H2O as the only byproducts making the protocol greener, atom economical and environmentally benign.

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Citations

Mar 30, 2019·Chemical Communications : Chem Comm·Jugal KishoreChidambaram Gunanathan
Oct 28, 2019·Angewandte Chemie·Akash KaithalWalter Leitner
May 7, 2020·Chemistry, an Asian Journal·Susanta HazraAnil J Elias
Oct 1, 2020·Chemical Communications : Chem Comm·Léo BettoniJean-Luc Renaud
Jun 27, 2019·ChemSusChem·Priyanka ChakrabortyBasker Sundararaju
Dec 23, 2020·ChemSusChem·Xiao-Bing LanZhuofeng Ke
Feb 23, 2021·Organic & Biomolecular Chemistry·Wei-Ze Li, Zhong-Xia Wang
Jun 1, 2021·ACS Central Science·Benjamin G Reed-BerendtLouis C Morrill
Jul 14, 2021·The Journal of Organic Chemistry·Biplab Keshari Pandia, Chidambaram Gunanathan
Feb 12, 2020·Organic Letters·Deepak Ranjan PradhanChidambaram Gunanathan
Apr 26, 2019·Organic Letters·Suhas Shahaji GawaliChidambaram Gunanathan
Nov 7, 2019·The Journal of Organic Chemistry·Artem A ZemtsovAlexander D Dilman
Oct 2, 2020·Organic Letters·Subramanian ThiyagarajanChidambaram Gunanathan
Aug 29, 2019·ACS Omega·Suhas Shahaji GawaliChidambaram Gunanathan
Sep 11, 2021·Organic Letters·Akash Bandu JamdadeBoopathy Gnanaprakasam
Sep 21, 2021·Chemical Communications : Chem Comm·Avijit MondalDipankar Srimani
Oct 28, 2021·Chemistry : a European Journal·Kai-Stephan FeichtnerViktoria H Gessner
Nov 25, 2021·The Journal of Organic Chemistry·Biplab Keshari PandiaChidambaram Gunanathan

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