Synthesis of azasilacyclopentenes and silanols via Huisgen cycloaddition-initiated C–H bond insertion cascades. Issue 10 (4th September 2017)

• Record Type: Journal Article
• Authors: Shih, Jiun-Le; Jansone-Popova, Santa; Huynh, Christopher; May, Jeremy A.
• Is Part Of: Chemical science. Volume 8:Issue 10(2017)
• Page Start: 7132
• Page End: 7137
• Publication Date: 2017-09-04
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c7sc03130k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Alkynyl carbonazidates form azasilacyclopentenes via a series of cyclizations, rearrangements, and an α-sily1 C–H bond insertion as determined by mechanistic investigations. Abstract : An unusual transition metal-free cascade reaction of alkynyl carbonazidates was discovered to form azasilacyclopentenes. Mild thermolysis afforded the products via a series of cyclizations, rearrangements, and an α-silyl C–H bond insertion (rather than the more common Wolff rearrangement, 1, 2-shift, or β-silyl C–H insertion) to form silacyclopropanes. A mechanistic proposal for the sequence was informed by control experiments and the characterization of reaction intermediates. The substrate scope and post-cascade transformations were also explored.