Alkynyl imines, which possess many reactive sites as well as alkenyl imines, are good substrate for the synthesis of various types of functionalized amine. However, the synthetic application of alkynyl imine has not been well studied so far. Therefore, we have studied the reaction of alkynyl oxime ether with radical species and nucleophiles. The carbon radical addition reaction of alkynyl oxime ether bearing the carbonyl group in the presence of Et3B as a radical initiator was firstly studied. The carbon radical attacked to b-position of alkynyl oxime ether to afford b-adduct in good to moderate yield, along with small amount of 1,2-adduct. The regioselective radical reaction was successfully extended to domino radical addition-aldol type reaction. On the other hand, the nucleophilic addition reaction with Et2CuLi led to complete inversion of regioselectivity giving a-adduct. Phenol and amines also reacted as a nucleophile at a-position.
