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Study on Oxidative Rearrangement of Ally Alcohols Directed toward Synthesis of Taxane-Type Natural Products

Research Project

Project/Area Number 06680550
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field Bioorganic chemistry
Research InstitutionInstitute for Chemical Reaction Science

Principal Investigator

KATO Michiharu  Institute for Chemical Reaction Science Professor, 反応化学研究所, 教授 (00006305)

Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1995: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1994: ¥1,500,000 (Direct Cost: ¥1,500,000)
Keywordsbicyclo [5.3.1] undecenones / intramolecular Barbier reaction / samarium iodide / (+) -nopinone / (+) -apoverbenone / (+) -verbenone / sulfenic acid elimination / 環外立体制御 / (+) -ノピノン / エナンチオ選択的合成 / 酸化的転位 / ブラシレノール / タキサン / 生物活性天然物
Research Abstract

1.In order to study oxidative transformation of 1-hydroxybicyclo [5.3.1] undec-2-enes into bicyclo [5.3.1] undec-1-en-2-ones, two types of starting materials, iodides and aldehydes, were prepared, that is, 5- (5-iodopentyl) cyclohex-2-en-1-one and 5- (3-oxo-4-cyclohexenyl) hexanal from 2-cyclohexenone, and 5- [2- (2-iodoethyl) benzyl] cyclohex-2-en-1-one and 2- [(3-oxo-4-cyclohexenyl) methyl] phenylethnal from 1,4-cyclohexadienone monoethylene acetal. However unfortunately, attempted intramolecular Barbier reaction of the above two iodides and cyclization reaction of the above two aldehydes with samarium iodide proved to be unsuccessful, and desired 1-hydroxybicyclo [5.3.1] undec-2-enes were scarcely obtainable. This is mostly because of great difficulty in eight membered ring formation by use of the above reaction conditions.
2.As part of utilization of (+) -nopinone toward enantioselective synthesis of natural products, chemical transformation of (+) -nopinone into (+) -apoverbenone and (+) -verbenone was examined. After all, the phenylsulfenylation-dehydrosulfenylation method was proved to be effective for this purpose, and (+) -apoverbenone and verbenone were prepared in high overall yields by use of this methodology.

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report

URL: 

Published: 1994-04-01   Modified: 2016-04-21  

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