| Project/Area Number |
02453084
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
TAKAHASHI Takashi Tokyo Institute of Technology, Department of Chemical Engineering, Associate Professor., 工学部, 助教授 (80110724)
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| Co-Investigator(Kenkyū-buntansha) |
YAMADA Haruo Tokyo Institute of Technology, Department of Chemical Engineering, Associate Pro, 工学部, 助手 (10175664)
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| Project Period (FY) |
1990 – 1991
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| Project Status |
Completed (Fiscal Year 1991)
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| Budget Amount *help |
¥5,500,000 (Direct Cost: ¥5,500,000)
Fiscal Year 1991: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1990: ¥4,700,000 (Direct Cost: ¥4,700,000)
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| Keywords | Neocarzinostatin Chromophore / Sarcophytol A / Protonation of the enolate / Transannular Diels-Alder reaction / Molecular mechanics / MM2 transition structure model / Conformational search / 中・大員環エノラ-ト / βー脱離反応 / ab initioーMM2遷移状態モデル / ジアニオン / NCS クロモフォア / ビラジカル / [2,3]ーWittig転位 / ペリプラノンJ. |
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| Research Abstract |
The objective of our research is to develop the suitable methods of calculations for the prediction (or analysis) of stereoselectivities in organic reactions and for designing of rational synthetic key intermediates. The methods such as molecular mechanics calculations including the systematic and/or random Monte Carlo conformational searches of synthetic intermediates and MM2 transition structure models for the protonation of the enolates, [2, 3]-Wittig rearrangement and Diels-Alder reaction were examined and found to be useful for this purpose.
We applied these methods to the following synthetic studies. 1)Synthesis of the highly strained bicyclo[7.3.0]diyne skeleton of neocarzinostatin chromophore using transannular[2, 3]-Wittig rearrangement of the 12-membered cyclic ether was achieved. The mechanistic investigations of Meyer's type transannular cyclization of 1 and Bergman cyclization of 2 were undertaken to generate the biradical species. 2)Total synthesis of sarcophytol A 3 which inhibits tumor promotion by teleocidin in two-stage carcinogenesis in mouse skin, was carried out based on the beta-elimination of the enolates on large membered ring system. 3)Synthesis of trans-hydrindanone 4 by conjugate addition-enolate protonation of the 3-alkyl-2-methyl-1-acetylcyclopentenone was examined. 4)Stereoselective transannular Diels-Alder reaction of 5 was examined to develop the general synthetic strategy for the tricyclic compounds. These types of so called "Prediction and Synthesis", where the theoretical calculations are validated by experimental results, are important for the development of the new synthetic strategies.
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