Convenient method for the functionalization of the 4- and 6-positions of the androgen skeleton

• Authors: Daniel Morton, Emory University; Allison R. Dick, State University of New York; Debashis Ghosh, State University of New York Syracuse; Huw Davies, Emory University
• Journal Title: Chemical Communications
• Volume: Volume 48, Number 47
• Publisher: Royal Society of Chemistry | 2012-06-14, Pages 5838-5840
• Type of Work: Article | Post-print: After Peer Review
• Publisher DOI: http://doi.org/10.1039/c2cc31973j
• Subjects: Chemistry, General
• Keywords: steroidal vinyldiazo compound; chemoselective entry; stereoselective synthesis; androgen analogue; dirhodium catalysis; silver catalysis; steroid skeleton

Abstract

The preparation and reactivity of steroidal vinyldiazo compounds is reported, providing a convenient, substituent tolerant, chemo- and stereoselective entry into 4- and 6-substituted androgen analogues from a common precursor. Under dirhodium catalysis, O—H insertion occurs at the carbenoid site, leading to 4-substituted steroids, but under silver catalysis, O—H insertion occurs at the vinylogous position, leading to 6-substituted steroids.