Stereocontrolled total synthesis of a polyfunctional carotenoid, peridinin.
Peridinin, which was isolated from the planktonic algae dinoflagellates causing red tides, is a highly oxidized carotenoid containing an allene and a characteristic (Z)-gamma-ylidenebutenolide function in the main conjugated polyene chain in addition to functionalized cyclohexane rings at both ends of the molecule. We achieved a stereocontrolled total synthesis of peridinin by featuring the Sharpless asymmetric epoxidation under precise reaction conditions, Wittig reaction with silylfuranmethylide followed by photosensitized oxygenation, stereocontrolled Pd-catalyzed one-pot (Z)-gamma-ylidenebutenolide synthesis, and modified Julia-Kocienski olefination. This synthesis is the first example of controlling the stereochemistry of polyfunctional allenic carotenoids.
Furuichi
Noriyuki
N
School of Science and Technology, Kwansei Gakuin University, Gakuen 2-1, Sanda, Hyogo 669-1337, Japan.
Hara
Hirokazu
H
Osaki
Takashi
T
Nakano
Masayuki
M
Mori
Hajime
H
Katsumura
Shigeo
S
D002338:Carotenoids / Q000138:chemical synthesis*; D002384:Catalysis; D007202:Indicators and Reagents; D019906:Nuclear Magnetic Resonance, Biomolecular; D010165:Palladium / Q000737:chemistry; D000461:Rhodophyta / Q000737:chemistry; D013237:Stereoisomerism
D007202:Indicators and Reagents; C016040:peridinin; D002338:Carotenoids; D010165:Palladium