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Chemistry of Epoxyquinols A, B, and C and Epoxytwinol A
Author(s) -
Shoji Mitsuru,
Hayashi Yujiro
Publication year - 2007
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200700092
Subject(s) - chemistry , kinetic resolution , cascade reaction , cycloaddition , furan , pyran , diene , biomimetic synthesis , total synthesis , diels–alder reaction , enantioselective synthesis , stereoselectivity , chemical synthesis , acryloyl chloride , organic chemistry , combinatorial chemistry , stereochemistry , catalysis , acrylate , natural rubber , polymer , monomer , biochemistry , in vitro
The asymmetric total synthesis of epoxyquinols A, B, and C and epoxytwinol A, and computational analysis of the key biomimetic oxidative dimerization procedure are described. In the first‐generation synthesis, a HfCl 4 ‐mediated diastereoselective Diels–Alder reaction of furan with Corey's chiral auxiliary has been developed. In the second‐generation synthesis, a chromatography‐free preparation of an iodolactone using acryloyl chloride as the dienophile in the Diels–Alder reaction of furan and a lipase‐mediated kinetic resolution of a cyclohexenol derivative have been developed. This second‐generation synthesis is suitable for large‐scale synthesis. A biomimetic cascade reaction involving oxidation, 6π‐electrocyclization, and then Diels–Alder dimerization is the key reaction in the formation of the complex heptacyclic structure of epoxyquinols A, B, and C. Epoxytwinol A is synthesized by the cascade reaction involving oxidation, 6π‐electrocyclization, and formal [4+4] cycloaddition reactions. A 2 H ‐pyran, generated by oxidation/6π‐electrocyclization, acts as a good diene, reacting with several dienophiles to afford polycyclic compounds in one step. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)