Divergent synthesis of polysubstituted cyclopropanes and β-silyoxy imidates via switchable additions of N-tert-butanesulfinylimidates to acylsilanes. Issue 26 (13th March 2019)

• Record Type: Journal Article
• Authors: Tang, Fan; Ma, Peng-Ju; Yao, Yun; Xu, Yan-Jun; Lu, Chong-Dao
• Is Part Of: Chemical communications. Volume 55:Issue 26(2019)
• Page Start: 3777
• Page End: 3780
• Publication Date: 2019-03-13
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c9cc00963a
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : A switchable addition of N-tert -butanesulfinylimidates to acylsilanes leads to divergent synthesis of polysubstituted cyclopropanes and β-silyloxy imidates. Abstract : Products derived from the reaction between N-tert -butanesulfinyl imidates and acylsilanes can be tuned by choosing appropriate bases and solvents. Here we show that in the presence of NaHMDS/THF, addition of enolized N-tert -butanesulfinyl imidates to acylsilanes and subsequent [1, 2]-Brook rearrangement generate β-silyloxy anion intermediates that undergo intramolecular cyclization to afford polysubstituted cyclopropanes. In the presence of t BuOK/toluene, the reaction generates β-silyloxy imidates as the protonation products of the β-silyloxy anion intermediates. Both reactions are highly diastereoselective.