Four- and Eight-Carbon Homologation of Benzaldehyde by (1Z,3Z)-Butyltelluro-1,3-Butadiene: Synthesis of Navenone B: Alarm Pheromone of the Mollusk Navanax inermis

Abstract Four- and eight-carbon homologation of benzaldehydes is described. The hydrotelluration of (Z)-1-methoxy-but-1-en-3-ynes 1 afforded (1Z,3Z)-1-butyltelluro-4-methoxy-1,3-butadiene 2, this compound 2 underwent a Te/Li exchange reaction, and the butadienyllithium 3 obtained reacted with benzaldehyde to form the corresponding allylic alcohol 4 with total retention of configuration. The allylic alcohol 4a formed underwent acidic hydrolysis, resulting in 5-phenyl-(2E,4E)-dienal 5 (four-carbon homologation of benzaldehyde). Product 5 reacted with the butadienyllithium 3, affording the alcohol 9-phenyl-(1Z,3Z,6E,8E)-1-methoxy-5-hydroxy-nonatetraene 6, which was hydrolyzed or spontaneously transformed into 9-phenyl-(2E,4E,6E,8E)-tetraenal 7, completing the eight-carbon homologation of benzaldehyde. Reaction of 9-phenyl-nona-(2E,4E,6E,8E)-tetraenal 7 with methyllithium in tetrahydrofuran afforded (3E,5E,7E,9E)-10-phenyl-deca-3,5,7,9-tetraen-2-ol 8. The product of the reaction described was employed in the ...