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Concise Synthesis of Anti-HIV-1 Active (+)-Inophyllum B and (+)-Calanolide A by Application of (−)-Quinine-Catalyzed Intramolecular Oxo-Michael Addition

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journal contribution
posted on 16.04.2004, 00:00 by Etsuko Sekino, Takuya Kumamoto, Tomohiro Tanaka, Tomoko Ikeda, Tsutomu Ishikawa
(−)-Quinine-catalyzed intramolecular oxo-Michael addition (IMA) of 7-hydroxy-5-methoxy-8-tigloylcoumarins was developed for the enantioselective construction of 2,3-dimethyl-4-chromanone systems in the context of the asymmetric synthesis of anti-HIV-1 active Calophyllum coumarins. Combination of the IMA and MgI2-assisted demethylation of the 5-methoxy group along with isomerization of the formed chromanone systems as key steps successfully led to the concise synthesis of (+)-inophyllum B and (+)-calanolide A, possible candidates for AIDS drugs. Further examination of the asymmetric IMA with cinchona alkaloids lacking a methoxy group on the quinoline skeleton suggested the influence of the methoxy substituent on stereoselectivity at the stereogenic centers of the chromanone systems.