Study on Stereoselective Synthesis of Biologically Active Substances Utilizing Organometallic Compounds

A serious side-reaction，proton transfer，which is usually observed in the conjugate addition to cyclopentenone(1)followed by alkylation of the resulting metal enolate(2)，as depicted in Scheme1，is eliminated by utilizing newly developed zincate(7)(Scheme2)。In the case of the conjugate addition of an excess&lt；plus-minus&gt；-cis omega-side chain，an efficient kinetic resolution takes place，giving Stereochemically homogeneous12(Scheme3Also，a novel cyclization is developed by an intramolecular olefin insertion to pi-allylic palladium complexes，and lied to the stereoselective synthesis of prostanoid frameworks with1，3-chirality transfer starting-divrotive.

A serious sideーreaction, proton transfer, which is usually observed in the conjugate addition to cyclopentenone (1) followed by alkylation of the resulting metal enolate (2), as depicted in Scheme 1, is eliminated by utilizing newly developed zincate (7) (Scheme 2). In the case of the conjugate addition of an excess <plus-minus>-cis omegaーside chain, an efficient kinetic resolution takes place, giving Stereochemically homogeneous 12 (Scheme 3Also, a novel cyclization is developed by an intramolecular olefin insertion to piーallylic palladium complexes, and applied to the stereoselective synthesis of prostanoid frameworks with 1, 3-chirality transfer starting from 3-oxoー8, 9-dihydroxytetradecaー1, 6-diene derivatives.