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

Abstract

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 β,β-carotene and (3R,3'R)-zeaxanthin (symmetrical) as well as 9-cis-β,β-carotene, 7,8-dihydro-β,β-carotene and β-cryptoxanthin (non-symmetrical).

Keywords: Hiyama-Denmark; carotenoids; cross-coupling; pentaenyl-bis-silanes; total synthesis.