A New Selective Allyl Transfer Reagent: Facile Entry to β-Hydroxy Enol Silyl Ethers Bearing Two Contiguous Stereogenic Centers

Abstract
η 3-Allyltitanium(III) complexes functionalized on the C-2 with a silyloxy group can be prepared by the reaction of titanocene dichloride with isopropylmagnesium chloride in the presence of the corresponding 2-silyloxybutadienes. These complexes undergo a highly regio- and diastereoselective addition with aldehydes to produce, depending on the treatment applied, anti diastereomeric β-hydroxy silyl enol ethers or β-hydroxy ketones. Two defined contiguous stereocenters make the enol silyl ethers containing them versatile synthons for further stereocontrolled transformations. The reaction constitutes a new method for directing electrophiles to the α-position of the α,β-enone system.

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