Studies on development of simple synthetic route for bioactive molecules utilizing of properties of SmI2

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The following results, (1) to (5), were provided. (1) The regioselectivity in SmI2-induced cascade reaction involving reductive coupling-Dieckmann type condensation of bis-alpha,beta-unsaturated carbonyl compounds was strongly influenced by steric hindrance of the group at C4 position and by difference of stability of each enolate generated by the initial reductive coupling. (2) The reaction condition of catalitic SmI2-induced cascade cyclization of bis-alpha,beta-unsaturated ester was found. And it was discovered that Sm was able to substitute by mischmetal in this cascade reaction. (3) Important synthetic intermediates for plant growth hormone gibberellin A3 were prepared via SmI2-induced cyclizations. (4) PDC catalyzed oxidative allylic rearrangement was developed. (5) A SmI2-induced novel rearrangement of bicyclo[4.2.0]octanones prepared by cycloaddition reaction of cyclohexenones with allene to produce bicyclo[3.2.1]octane derivatives was developed.