Chelation and Stereodirecting Group Effects on Regio- and Diastereoselective Samarium(II)-Water Allylic Benzoate Reductions

Abstract

SmI₂(H₂O)_n reductions of allylic benzoates adjacent to a trisubstituted alkene occur in high yields with complete regioselectivity and good diastereoselectivity (up to 90:10) for substrates containing properly positioned stereodirecting- and chelating groups. The outcome of these reactions can be rationalized by ring conformation considerations of a proposed chelated organosamarium intermediate, and a mechanism involving intramolecular protonation by a samarium-bound water.

Key words

samarium - reduction - diastereoselective - regioselective - chelation

• References

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