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

• Type of Material: Article
• 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
• Language: English
• Date: 2012-06-14
• Publisher: Royal Society of Chemistry
• Publication Version: Author Accepted Manuscript (After Peer Review)
• Copyright Statement: © The Royal Society of Chemistry 2012
• Final Published Version (URL): http://pubs.rsc.org/en/Content/ArticleLanding/2012/CC/c2cc31973j
• Title of Journal or Parent Work: Chemical Communications
• ISSN: 1359-7345
• Volume: 48
• Issue: 47
• Start Page: 5838
• End Page: 5840
• Grant/Funding Information: This research was supported by the National Institutes of Health (R01GM086893).
• Keywords: silver catalysis; androgen analogue; steroidal vinyldiazo compound; stereoselective synthesis; steroid skeleton; chemoselective entry; dirhodium catalysis
• Research Categories: Chemistry, General

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.