1,3-Allylic strain as a control element in the Paterno-Buchi reaction of chiral silyl enol ethers: Synthesis of diastereomerically pure oxetanes containing four contiguous stereogenic centers

Thorsten Bach, Kai Jödicke, Kristian Kather, Roland Fröhlich

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Abstract

The facial diastereoselectivity in the Paterno-Buchi reaction of chiral silyl enol ethers and benzaldehyde was studied. The substituents (R(S),R(L)) at the stereogenic carbon atom (-C*HR(S)R(L)) attached to the β-position of the silyl enol ether were varied in order to evaluate the influence of steric bulk and electronic effects. The combined yields for the two diastereomeric 3-(silyloxy)oxetanes a and b range between 44% and 76%. In accordance with the 1,3-allylic strain model the facial diastereoselectivity (diastereomeric ratio (dr) = a/b) was best with large (R(L) = t-Bu, SiMe2Ph) and polar (R(L) = OMe) substituents at the γ-position of the silyl enol ether (dr up to > 95/5). Two regioselective ring opening reactions were applied to the product oxetanes 29a, 50, and 51. They furnished diastereomerically pure diols (52, 53) and triols (31) in excellent yields.

Original languageEnglish
Pages (from-to)2437-2445
Number of pages9
JournalJournal of the American Chemical Society
Volume119
Issue number10
DOIs
StatePublished - 12 Mar 1997
Externally publishedYes

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