Diastereoselective synthesis of trisubstituted olefins using a silicon-tether ring-closing metathesis strategy. Issue 12 (11th March 2020)

• Record Type: Journal Article
• Authors: Wittmann, Stéphane; Tiniakos, Alexander F.; Prunet, Joëlle
• Is Part Of: Organic & biomolecular chemistry. Volume 18:Issue 12(2020)
• Page Start: 2297
• Page End: 2306
• Publication Date: 2020-03-11
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c9ob02563d
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : We report an efficient and diastereoselective synthesis of E - and Z -trisubstituted alkenes by a silicon-tether ring-closing metathesis strategy. Abstract : The diastereoselective synthesis of trisubstituted olefins with concomitant C–C bond formation is still a difficult challenge, and olefin metathesis reactions for the formation of such alkenes are usually not high yielding or/and diastereoselective. Herein we report an efficient and diastereoselective synthesis of trisubstituted olefins flanked by an allylic alcohol, by a silicon-tether ring-closing metathesis strategy. Both E - and Z -trisubstituted alkenes were synthesised, depending on the method employed to cleave the silicon tether. Furthermore, this methodology features a novel Peterson olefination for the synthesis of allyldimethylsilanes. These versatile intermediates were also converted into the corresponding allylchlorodimethylsilanes, which are not easily accessible in high yields by other methods.