Modular Approach to Reductive C(sp2)-H and C(sp3)-H Silylation of Carboxylic Acid Derivatives through Single-Pot, Sequential Transition Metal Catalysis

Yuanda Hua; Seongjeong Jung; James Roh; Junha Jeon

doi:10.1021/acs.joc.5b00564

Modular Approach to Reductive C(sp2)-H and C(sp3)-H Silylation of Carboxylic Acid Derivatives through Single-Pot, Sequential Transition Metal Catalysis

J Org Chem. 2015 May 1;80(9):4661-71. doi: 10.1021/acs.joc.5b00564. Epub 2015 Apr 16.

Authors

Yuanda Hua¹, Seongjeong Jung¹, James Roh¹, Junha Jeon¹

Affiliation

¹ Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington, Texas 76019, United States.

PMID: 25853682
DOI: 10.1021/acs.joc.5b00564

Abstract

We report a modular approach to catalytic reductive Csp2-H and Csp3-H silylation of carboxylic acid derivatives encompassing esters, ketones, and aldehydes. Choice of either an Ir(I)/Rh(I) or Rh(I)/Rh(I) sequence leads to either exhaustive reductive ester or reductive ketone/aldehyde silylation, respectively. Notably, a catalyst-controlled direct formation of doubly reduced silyl ethers is presented, specifically via Ir-catalyzed exhaustive hydrosilylation. The resulting silyl ethers undergo Csp2-H and benzylic Csp3-H silylation in a single vessel.