Abstract
The asymmetric total synthesis of epoxyquinols A, B, and C, and epoxytwinol A, and computational analysis of the key biomimetic oxidative dimerization, are described. In the first-generation synthesis, the HfC l4-mediated diastereoselective Diels-Alder reaction of furan with chiral acrylate has been developed. In the second-generation synthesis, a chromatography-free preparation of an iodolactone by using acryloyl chloride as the dienophile in the Diels-Alder reaction of furan, and the lipase-mediated kinetic resolution of a cyclohexenol derivative have been developed. A biomimetic cascade reaction involving oxidation, 6π-electrocyclization, and Diels-Alder dimerization or formal [4 + 4] cycloaddition, is the key reaction in the formation of heptacyclic structure of epoxyquinols A, B, and C, and epoxytwinol A. Intermolecular hydrogen-bonding is found to be the key, causing formation of both epoxyquinols A and B. In the dimerization of epoxyquinol monomer, two monomeric 2H-pyrans interact each other to afford pre-associated complexes stabilized by hydrogen-bonding, then Diels-Alder reaction proceeds.
| Original language | English |
|---|---|
| Pages (from-to) | 102-113 |
| Number of pages | 12 |
| Journal | Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry |
| Volume | 67 |
| Issue number | 2 |
| Publication status | Published - 2009 Feb |
| Externally published | Yes |
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Keywords
- DFT analysis
- Diels-Alder reaction
- Epoxyquinols A-C
- Epoxytwinol A
- Hafnium tetrachloride
- Lipase-mediated kinetic resolution
- Oxidative dimerization
ASJC Scopus subject areas
- Organic Chemistry
Cite this
Total synthesis of epoxyquinols : Oxidative dimerization and its theoretical analysis. / Shoji, Mitsuru; Hayashi, Yujiro.
In: Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, Vol. 67, No. 2, 02.2009, p. 102-113.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Total synthesis of epoxyquinols
T2 - Oxidative dimerization and its theoretical analysis
AU - Shoji, Mitsuru
AU - Hayashi, Yujiro
PY - 2009/2
Y1 - 2009/2
N2 - The asymmetric total synthesis of epoxyquinols A, B, and C, and epoxytwinol A, and computational analysis of the key biomimetic oxidative dimerization, are described. In the first-generation synthesis, the HfC l4-mediated diastereoselective Diels-Alder reaction of furan with chiral acrylate has been developed. In the second-generation synthesis, a chromatography-free preparation of an iodolactone by using acryloyl chloride as the dienophile in the Diels-Alder reaction of furan, and the lipase-mediated kinetic resolution of a cyclohexenol derivative have been developed. A biomimetic cascade reaction involving oxidation, 6π-electrocyclization, and Diels-Alder dimerization or formal [4 + 4] cycloaddition, is the key reaction in the formation of heptacyclic structure of epoxyquinols A, B, and C, and epoxytwinol A. Intermolecular hydrogen-bonding is found to be the key, causing formation of both epoxyquinols A and B. In the dimerization of epoxyquinol monomer, two monomeric 2H-pyrans interact each other to afford pre-associated complexes stabilized by hydrogen-bonding, then Diels-Alder reaction proceeds.
AB - The asymmetric total synthesis of epoxyquinols A, B, and C, and epoxytwinol A, and computational analysis of the key biomimetic oxidative dimerization, are described. In the first-generation synthesis, the HfC l4-mediated diastereoselective Diels-Alder reaction of furan with chiral acrylate has been developed. In the second-generation synthesis, a chromatography-free preparation of an iodolactone by using acryloyl chloride as the dienophile in the Diels-Alder reaction of furan, and the lipase-mediated kinetic resolution of a cyclohexenol derivative have been developed. A biomimetic cascade reaction involving oxidation, 6π-electrocyclization, and Diels-Alder dimerization or formal [4 + 4] cycloaddition, is the key reaction in the formation of heptacyclic structure of epoxyquinols A, B, and C, and epoxytwinol A. Intermolecular hydrogen-bonding is found to be the key, causing formation of both epoxyquinols A and B. In the dimerization of epoxyquinol monomer, two monomeric 2H-pyrans interact each other to afford pre-associated complexes stabilized by hydrogen-bonding, then Diels-Alder reaction proceeds.
KW - DFT analysis
KW - Diels-Alder reaction
KW - Epoxyquinols A-C
KW - Epoxytwinol A
KW - Hafnium tetrachloride
KW - Lipase-mediated kinetic resolution
KW - Oxidative dimerization
UR - http://www.scopus.com/inward/record.url?scp=65449143632&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=65449143632&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:65449143632
VL - 67
SP - 102
EP - 113
JO - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
JF - Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
SN - 0037-9980
IS - 2
ER -