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

烯丙醇氧化重排合成紫杉烷类天然产物的研究

• 批准号: 06680550
• 负责人: KATO Michiharu
• 金额: $ 1.34万
• 依托单位: Institute for Chemical Reaction Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06680550/
• 关键词: bicyclo [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

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.

1.为了研究1-羟基双环[5.3.1]十一烯-2-烯氧化转化为二环[5.3.1]十一烯-1-en-2-酮，制备了碘化物和醛两种起始原料，即5-(5-碘戊基)环己-2-en-1-酮和5-(3-氧代-4-环己烯基) 己醛来自2-环己烯酮，5-[2-(2-碘乙基)苄基]环己-2-en-1-酮和2-[(3-氧代-4-环己烯基)甲基]苯基乙醛来自1,4-环己二烯酮单乙烯缩醛。然而不幸的是，尝试上述两种碘化物的分子内巴比尔反应以及上述两种醛与碘化钐的环化反应被证明是不成功的，并且几乎无法获得所需的1-羟基双环[5.3.1]十一碳-2-烯。这主要是因为使用上述反应条件形成八元环非常困难。2.作为利用(+)-诺品酮对映选择性合成天然产物的一部分，研究了(+)-诺品酮向(+)-阿维苯酮和(+)-马鞭草酮的化学转化。毕竟，苯磺酰化-脱氢磺酰化方法被证明对于此目的是有效的，并且通过使用该方法以高总产率制备了(+)-apoverbenone和马鞭草酮。