Rhodium-Catalyzed Regioselective Silylation of Alkyl C-H Bonds for the Synthesis of 1,4-Diols.

ABSTRACT: A rhodium-catalyzed intramolecular silylation of alkyl C-H bonds has been developed that occurs with unusual selectivity for the C-H bonds located δ to the oxygen atom of an alcohol-derived silyl ether over typically more reactive C-H bonds more proximal to the same oxygen atom. (Hydrido)silyl ethers, generated in situ by dehydrogenative coupling of tertiary alcohols with diethylsilane, undergo regioselective silylation at a primary C-H bond δ to the hydroxyl group in the presence of [(Xantphos)Rh(Cl)] as catalyst. Oxidation of the resulting 6-membered oxasilolanes generates 1,4-diols. This silylation and oxidation sequence provides an efficient method to synthesize 1,4-diols by a hydroxyl-directed, aliphatic C-H bond functionalization reaction and is distinct from the synthesis of 1,3-dio

SUBMITTER: Karmel C 

PROVIDER: S-EPMC5810544 | biostudies-literature | 2018 Jan

REPOSITORIES: biostudies-literature