Bidirectional Hiyama-Denmark Cross-Coupling Reactions of Bissilyldeca-1,3,5,7,9-pentaenes for the Synthesis of Symmetrical and Non-Symmetrical Carotenoids.

The construction of the carotenoid skeleton by Pd-catalyzed Csp2 -Csp2 cross-coupling reactions of symmetrical and non-symmetrical 1,10-bissilyldeca-1,3,5,7,9-pentaenes and the corresponding complementary alkenyl iodides has been developed. Reaction conditions for these bidirectional and orthogonal Hiyama-Denmark cross-coupling reactions of bisfunctionalized pentaenes are mild and the carotenoid products preserve the stereochemical information of the corresponding oligoene partners. The carotenoids synthesized in this manner include ß,ß-carotene and (3R,3'R)-zeaxanthin (symmetrical) as well as 9-cis-ß,ß-carotene, 7,8-dihydro-ß,ß-carotene and ß-cryptoxanthin (non-symmetrical).