| Project/Area Number |
63570985
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
Chemical pharmacy
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| Research Institution | Toyama Medical & Pharmaceutical University |
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Principal Investigator |
KOIZUMI Toru Faculty of Pharm. Sci., Synthetic Org. Chem. Professor, 薬学部, 教授 (40012611)
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| Co-Investigator(Kenkyū-buntansha) |
TAKAHASHI Tamiko Fac. of Pharm. Sci., Synthetic Org. Chem. Assistant Prf, 薬学部, 助手 (10115181)
ARAI Yoshitsugu Fac. of Pharm. Sci., Synthetic Org. Chem. Assistant Prf, 薬学部, 助手 (10115157)
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| Project Period (FY) |
1988 – 1989
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| Project Status |
Completed (Fiscal Year 1989)
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| Budget Amount *help |
¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1989: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1988: ¥1,400,000 (Direct Cost: ¥1,400,000)
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| Keywords | CHIRAL DIENOPHILE / CHIRAL SULFINYL ETHENE / ASYMMETRIC DIELS-ALDER REACTION / DIASTEREOSELECTIVITY / キラル合成 / キラルジェノフィル / キラルスルホキシド / スルフィニルエテン / 生物活性物質 / 不斉環化付加反応 / ディールス・アルダー反応 |
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| Research Abstract |
Utilizing cycloadducts which were obtained by the Diels-Alder reaction of (R)_s-2-methyl-3-( p-tolylsulfinyl )p ropenoate (A) and menthyl 3-(2-pyridylsulfinyl) acrylate (B) with cyclopentadiene, chiral synthesis of (+)-epi-beta-santalene (ref 1) , (-)-aristeromycin and (-)-neplanocin A (ref 3) were accomplished. Furthermore, starting from the adduct obtained from the cycloaddition of dienophile B and furan , chiral synthesis of (-)-shikimic acid and epi-shikimic acid were achieved (ref. 2 & 6). An important key intermediate for the synthesis of polycyclopenatano ids have been obtained by the D-A reaction of B and cyclohexadiene (ref. 4)
On the other hand, dimethyl (R)_s-2-(isoborneol-10-sulfinyl) acrylate (C) has been designed and obtained diastereoselectively starting from dimethyl acetylenedicarboxylate and 1-mercapto- isoborneol. Under the presence of Lewis acid catalyst, the D-A reaction of the dienophile C with cyclopentadiene proceeded highly stereo- and diastereoselective manner to afford a single adduct, which was effectively converted to Ohno's half ester (ref. 5). Since the Ohno's half ester have been transformed into various carbocyclic nucleosides, the present synthesis constitutes the formal synthesis of those carbocyclic nucleosides and would find wide applications.
During this investigation, we found 10-mercaptoisoborneol could be a good chiral auxiliary for the synthesis of optically active alkyl sulfoxides, in general (ref. 10). The thiol also turned out to be an excellent chiral auxiliary for the synthesis of optically active organophosphorus compounds (ref 9).
Meanwhile, the cycloaddition of 1-methyl-3-oxidopyridinium with various sulfinyl ethenes has been studied. The adducts were effectively converted to 2alpha-tropanol derivatives both in racemic and optically active forms (ref. 7, 8).
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