Palladium-Catalyzed Desilylative Acyloxylation of Silicon-Carbon Bonds on (Trimethylsilyl)arenes: Synthesis of Phenol Derivatives from Trimethylsilylarenes

Keisuke Gondo; Juzo Oyamada; Tsugio Kitamura

doi:10.1021/acs.orglett.5b02336

Palladium-Catalyzed Desilylative Acyloxylation of Silicon-Carbon Bonds on (Trimethylsilyl)arenes: Synthesis of Phenol Derivatives from Trimethylsilylarenes

Org Lett. 2015 Oct 2;17(19):4778-81. doi: 10.1021/acs.orglett.5b02336.

Authors

Keisuke Gondo¹, Juzo Oyamada¹, Tsugio Kitamura¹

Affiliation

¹ Department of Chemistry and Applied Chemistry, Graduate School of Science and Engineering, Saga University , Honjo-machi, Saga 840-8502, Japan.

PMID: 26401835
DOI: 10.1021/acs.orglett.5b02336

Abstract

A strategy for desilylative acetoxylation of (trimethylsilyl)arenes has been developed in which (trimethylsilyl)arenes are converted into acetoxyarenes. The direct acetoxylation is performed in the presence of 5 mol % of Pd(OAc)2 and PhI(OCOCF3)2 (1.5 equiv) in AcOH at 80 °C for 17 h. The acetoxyarenes are obtained in good to high yields (67-98%). The synthetic utility is demonstrated with a one-pot transformation of (trimethylsilyl)arenes to phenols by successive acetoxylation and hydrolysis. Furthermore, desilylative acyloxylation of 2-(trimethylsilyl)naphthalene using several carboxylic acids has been conducted.