1991 Fiscal Year Final Research Report Summary
Development of a General Method for Synthesis of Optically Active Tertiarv Allylic Alcohols and Its Applications
| Project/Area Number |
02453091
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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 |
Synthetic chemistry
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
SATO Fumie Tokyo Institute of Technology, Biomolecular Engineering, Professor, 生命理工学部, 教授 (50016606)
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| Co-Investigator(Kenkyū-buntansha) |
OKAMOTO Sentaro Tokyo Institute of Technology Biomolecular Engineering, Research Associate, 生命理工学部, 助手 (00201989)
KOBAYASHI Yuichi Tokyo Institute of Technology Biomolecular Engineering, Associate Professor, 生命理工学部, 助教授 (90153650)
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| Project Period (FY) |
1990 – 1991
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| Keywords | Chiral / Asymmetric Synthesis / Allylic Alcohols / Tertiary Alcohols / Prostaglandin / Arbaprostil / Epoxy Alcohol |
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| Research Abstract |
Tertiary allylic alcohols are incorporated in the structures of a variety of natural products and commercially important pharmaceuticals. Equally significant is the latent faculties of tertiary allylic alcohols as versatile synthetic intermediates. Only a few methods, however, are available for preparation of them in a chiral form and these methods so far developed suffer from some disadvantages such as low optical purity and/or lack of generality. We have now succeeded in developing practical and general synthetic method of tertiary allylic alcohols.
Thus, the reaction of beta-trimethylsilyl-alpha, beta-epoxyketones, readily prepared in a chiral form by using the Sharpless kinetic resolution of gamma-trimethytsilyl secondary allylic alcohols as a key reaction, with Grignard reagents proceeds highly diastereoselectively to afford optically active gamma-trimethylsilyl-beta, gamma-epoxy tertiary alcohols. gamma-Trimethylsilyl-beta, gamma-epoxy tertiary alcohols reacts with nucleophils affords the corresponding tertiary allylic alcohols via regionspecific ring opening followed by the Peterson olefination reaction. The application of the tertiary allylic alcohols thus obtained to the synthesis of prostaglandin derivative, Arbaprostil was carried out.
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