Diastereoselective Temporary Silicon-Tethered Ring-Closing-Metathesis Reactions with Prochiral Alcohols: A New Approach to Long-Range Asymmetric Induction

Authors


  • We sincerely thank the National Institutes of Health (GM54623) for generous financial support. We also thank Johnson and Johnson for a Focused Giving Award, Pfizer Pharmaceuticals for the Creativity in Organic Chemistry Award, and Novartis Pharmaceuticals for an Academic Achievement Award. The Camille and Henry Dreyfus Foundation is thanked for a Camille Dreyfus Teacher-Scholar Award (P.A.E.).

Abstract

original image

A useful approach to 1,4-, 1,5-, and 1,6-stereocontrol, diastereoselective ring-closing-metathesis reactions that utilize temporary silicon tethers represent a new strategy for long-range asymmetric induction. This method facilitates the construction of cis-1,4-silaketals (n=0, d.r.=20:1; see scheme), whereas the extension of this concept to higher alkenyl alcohols (n=1–4) results in a reversal of diastereoselectivity that favors formation of the trans isomer.

Ancillary