Premium
Total Synthesis of Peridinin and Related C 37 ‐Norcarotenoid Butenolides
Author(s) -
Vaz Belén,
Domínguez Marta,
Alvarez Rosana,
de Lera Angel R.
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600959
Subject(s) - polyene , peridinin , stille reaction , isomerization , stereochemistry , total synthesis , chemistry , double bond , carotenoid , organic chemistry , fucoxanthin , food science , catalysis , polymer
As an extension of our synthesis of symmetrical carotenoids, the preparation of the highly functionalized C 37 ‐norcarotenoid butenolide peridinin ( 1 ), its 6′‐ epi ‐ and 11′ Z stereoisomers has been completed. Featuring a central dihalogenated C 8 linchpin unit 6 , two synthetic routes, differing in the ordering of the last three steps were explored by using the C3,C3′‐bisdehydroxylated target as the model system. The first route uses the combination of a modified Z ‐selective Julia reaction and two sequential Stille couplings, the last one producing the isomerisation of the polyene Z double bond. The second route inverts these steps and makes the isolation of the 11′ Z stereoisomers as major products possible. An efficient Z to E isomerisation of the final carotenoid skeleton simply uses the Stille reaction conditions at ambient temperature. As the reaction of bromoallene 12 with alkenylstannane 11 occurs with inversion of configuration, 6′‐ epi ‐peridinin could also be prepared by route A. The advantages and limitations of the sequential Stille cross‐coupling approach to carotenoids are highlighted.