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 |
| Externally published | Yes |
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Keywords
- Density functional calculations
- Diels-Alder reactions
- Electrocyclic reactions
- Epoxyquinols A, B, C
- Epoxytwinol A
- Total synthesis
ASJC Scopus subject areas
- Organic Chemistry
Cite this
Chemistry of epoxyquinols A, B, and C and epoxytwinol A. / Shoji, Mitsuru; Hayashi, Yujiro.
In: European Journal of Organic Chemistry, No. 23, 2007, p. 3783-3800.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Chemistry of epoxyquinols A, B, and C and epoxytwinol A
AU - Shoji, Mitsuru
AU - Hayashi, Yujiro
PY - 2007
Y1 - 2007
N2 - 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.
AB - 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.
KW - Density functional calculations
KW - Diels-Alder reactions
KW - Electrocyclic reactions
KW - Epoxyquinols A, B, C
KW - Epoxytwinol A
KW - Total synthesis
UR - http://www.scopus.com/inward/record.url?scp=34547776294&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=34547776294&partnerID=8YFLogxK
U2 - 10.1002/ejoc.200700092
DO - 10.1002/ejoc.200700092
M3 - Article
SP - 3783
EP - 3800
JO - Annalen der Pharmacie
JF - Annalen der Pharmacie
SN - 0365-5490
IS - 23
ER -