Grant-in-Aid for Scientific Research (A).
|Research Institution||Nagoya University, School Engineering|
EGUCHI Shoji NAGOYA UNIV., DEPT.OF APPLIED CHEM., PROF., 工学部, 教授 (50023099)
OKANO Takashi NAGOYA UNIV., DEPT.OF APPLIED CHEM., ASSISTANTPROF., 工学部, 助手 (90194373)
OHNO Masatomi NAGOYA UNIV., DEPT.OF APPLIED CHEM., ASSOCIATEPROF., 工学部, 助教授 (50072682)
MINAMOTO Katsumaro NAGOYA UNIV., DEPT.OF APPLIED CHEM., PROF., 工学部, 教授 (50023106)
|Project Fiscal Year
1992 – 1994
Completed(Fiscal Year 1994)
|Budget Amount *help
¥35,400,000 (Direct Cost : ¥35,400,000)
Fiscal Year 1994 : ¥3,100,000 (Direct Cost : ¥3,100,000)
Fiscal Year 1993 : ¥6,400,000 (Direct Cost : ¥6,400,000)
Fiscal Year 1992 : ¥25,900,000 (Direct Cost : ¥25,900,000)
|Keywords||iminophosphorane / aza-Wittig reaction / nitrone / difluoromethylene group / trifluoromethyl group / squaric acid / uracil / thymine / イミノホスホラン / aza-Witttig反応 / ニトロン / ジフルオロメチレン基 / トリフルオロメチル基 / スクアリン酸 / ウラシル / チミン / 1,3-双極性環化付加反応 / 1,2,4-オキサジアゾリン / ハロヌクレオシド / ジフルオロカルボン酸 / aza-Wittig反応 / ニオロオレフィン / アザーウィッチッヒ反応 / ジヒドロキナゾリン / ニトリル / アジドヌクレオシド / ジフルオロアリルカルボニル / アザマクロサイクル / 1,4-ベンゾジアゼピノン / ピリミジン誘導体 / シクロヌクレオシド / キナゾリノン増環反応 / 還元的環拡大反応|
Synthetic designing of novel heteropolycycles, in particular N containing systems, has been carried out to provide the chemical base of new materials potentially useful in future industry. The results are summarized below.
1. Design of Nitrogen Heterocycles by Using Iminophosphorane.
Both enantiomers of quinazoline alkaloid, Vasicinone are prepared via asymetric oxidation of deoxyvasicinone which is efficiently obtainable by intramolecular aza-Wittig reaction. Quinazoline antitumor agent Batracylin and antitumor antibiotics DC-81 were synthesized via intramolecular aza-Wittig methodology. A new synthesis of pteridine derivatives has been developed by intermolecular aza-Wittig reaction followed by heterocyclization.
2. Desgin of Novel Polycyclo-type Heterocycles by Cycloaddition. Design of Polycyclo-type Nitrones and Their Reaction. Nitrones inbeded in homoadamantane frame exhibited unique reactivity with alkynes and nitriies. With alkynes they gave homoadamantane-fused isoxazolines which
rearranged themally to fused pyrroies and with nitriies they cycloadded to afford 2,3-dihydro-1,2,4-oxadiazoles, that provided a general and direct route to such novel heterocycles.
3. Design of Synthetic Blocks containing Organofluorine Function and Their Application.
Difluoromethylene compounds such as alpha, alpha-difluoro-carboxylic acids and-ketones have been designed by utilizing radical addition. alpha, alpha-Difluoro-gamma-amino butyric acid and difluoropyridones were synthesized by this method. Trifluoromethylated 5-and 6-membered N heterocycles have been synthesized using trifluoromethyl-1,3-diketone and-enamides.
4. Molecular Design by Small Ring Compounds. Suaric Acid Derivatives.
Squaric acid derivatives have been designed and they were converted to substituted gamma-butenolides, furanones and bicyclo [3.2.0] heptenones via thermal as well as newly found radical ring-opening followed by recyclization scheme. New efficient synthetic routes to biologically active natural products, (E) -basidalin and (Z) -multicolanate have been developed utilizing above ring-transformation as the key step.
5. Molecular Design of Chemically Modified Nucleosides.
Thymine and uracil were modified by introducing amino, bromo and nitro functions to the 2-and/or 3-positions of the furanose and pyranose sugar moieties. 2,2'-Anhydro derivatives of thimine was also utilized for the stereo and regio-selective introduction of these functions to the pyrimidine base.
6. Physical and Biological Properties of Designed Heteropolycycles.
Datailed physical and biological properties of these new compounds prepared above are future projects.