N,2-DILITHIOALKYLAMINES FROM AZIRIDINES BY NAPHTHALENE-CATALYZED REDUCTIVE OPENING - SYNTHETIC APPLICATIONS

The reductive opening of aziridines 1a-c with lithium in the presence of a catalytic amount of naphthalene at -78 degrees C led to the corre sponding dianionic intermediates 2a-c, which are stable species under these reaction conditions and react with electrophilic reagents [H2O, D2O, Me(2)S(2), Bu(t)CHO, PhCHO, Me(2)CO, (CH2)(5)CO, (EtO)(2)CO, CH2= CHCO(2)Me, PhCON(CH2)(4), PhCH=NPh, MeI, and CH2=CHCH2Br] to give, aft er hydrolysis with water, the corresponding difunctionalized compounds 3-5. When the reductive opening and the reaction with electrophiles [ H2O, D2O, CH2=CHCH2Br, Me(2)CO, (c-C3H5)(2)CO] were carried out on chi ral aziridines 8 and 9, enantiomerically pure difunctionalized compoun ds 12 were obtained with same stereochemistry, independently of the st ereochemistry of diastereomeric starting aziridines 8 and 9.