Abstract
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 2H-pyran, generated by oxidation/6π-electrocyclization, acts as a good diene, reacting with several dienophiles to afford polycyclic compounds in one step.
Original language | English |
---|---|
Pages (from-to) | 3783-3800 |
Number of pages | 18 |
Journal | European Journal of Organic Chemistry |
Issue number | 23 |
DOIs | |
Publication status | Published - 2007 Aug 16 |
Keywords
- Density functional calculations
- Diels-Alder reactions
- Electrocyclic reactions
- Epoxyquinols A, B, C
- Epoxytwinol A
- Total synthesis
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry