Total syntheses of (-)-fructigenine A and (-)-5-N-acetylardeemin.
The first total synthesis of (-)-fructigenine A and a novel approach to (-)-5-N-acetylardeemin through a common imine intermediate (+)-3 are described. The key steps include highly enantioselective preparation of (+)-3 via domino olefination/isomerization/Claisen rearrangement (OIC) of 5, reductive cyclization (RC), and regioselective oxidation of (-)-4 and a novel assembly of the pyrazino ring of these alkaloids via Ugi three-component reaction/cyclization of (+)-3 with the corresponding amino acid and isonitrile.
Takiguchi
Satoshi
S
Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan.
Iizuka
Toshimasa
T
Kumakura
Yuh-suke
YS
Murasaki
Kohta
K
Ban
Naoko
N
Higuchi
Kazuhiro
K
Kawasaki
Tomomi
T
D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010084:Oxidation-Reduction; D011744:Pyrimidinones; D013237:Stereoisomerism
D000470:Alkaloids; D006576:Heterocyclic Compounds, 4 or More Rings; D011744:Pyrimidinones; C549274:fructigenine A; C080891:5-N-acetylardeemin