電気化学的手法による高立体・配向選択的合成法の開発と生理活性化合物合成への展開

电化学方法开发高度立体和定向选择性合成方法及其在生物活性化合物合成中的应用

• 批准号: 06226208
• 负责人: 福本 圭一郎
• 金额: $ 1.6万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 无数据
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06226208/
• 关键词: electron-transfer catalyst; alkaloid synthesis; indirect electroreductive cyclization; VB_<12a>; Ni(ll)complex; ipecac alkaloid; η-bromo-α,β-unsaturated esters

平成5年度に得られた活性種発生法と炭素-炭素結合生成法の開発を踏まえ、本年度は電極との間での電子授受の容易な基質の探索と活性種の構造を検討し、より有用な官能基を明らかにしえた。次いで基質に構造化学的修飾を加え、立体選択性、配向選択性並びに位置選択性についての検討を加え、より効率的な反応へと導き、併せてキラル補助剤存在下での反応を行い、アルカロイドのツブロシンの全合成を完成した。更に電解条件下でのハロゲン化不飽和エステルを用いる分子内Michael反応にいて、試薬を用いる化学反応、光反応、熱反応、並びに金属試薬存在下における反応と比較し、電気化学的手法の特長を引き出することに成功し、脳血管拡張作用の期待されるツブロシンの全合成を達成した。

In 2005, the development of active species generation method and carbon-carbon combination generation method was carried out. In 2005, the exploration of electron transfer and active species structure was carried out, and the useful functional groups were clearly identified. The second is the addition of structural chemical modification, stereoselectivity, alignment selectivity and positional selectivity of the matrix, the addition of effective reaction and guidance, and the completion of total synthesis of reaction and reaction in the presence of auxiliary agents. In addition, under electrolytic conditions, the reaction of unsaturated molecules in intramolecular Michael reaction, chemical reaction, optical reaction, thermal reaction, and metal reaction in the presence of chemical reaction, electrochemical reaction, and chemical reaction were successfully introduced.

项目成果

井原 正隆: "Indirect Electroreductive Cyclization for Syntheses of Key Intermediates of Several Indole and Ipecac Alkaloids" CHEM.PHARM.BULL. 43. 362-364 (1995)

Masataka Ihara：“间接电还原环化合成几种吲哚和吐根生物碱的关键中间体”CHEM.PHARM.BULL 43. 362-364 (1995)

"Stereoselective Formation of Three Carbon-Carbon Bonds by Cascade Reaction with Enolate Anion:Synthesis of Tricyclo〔6.2.0_<1.6>〕dodecan and Tricyclo〔5.3.1.0_<3.8>〕undecane Derivatives" J.Org.Ghem.59. 6008-6013 (1994)

“通过烯醇阴离子级联反应立体选择性形成三个碳-碳键：三环[6.2.0_<1.6>]十二烷和三环[5.3.1.0_<3.8>]十一烷衍生物的合成”J.Org.Ghem.59。 6008-6013 (1994)

井原 正隆: "Construction of Polycyclic Ring Systems Fused to Cyclobutane by Sequential Three Reactions,Opening of Three Membered Ring-Michael Aldol Sequence" Tetrahedron Lett.35. 1901-1904 (1994)

Masataka Ihara：“通过连续三个反应构建与环丁烷稠合的多环系统，三元环迈克尔醇醛序列的开环”四面体快报 1901-1904 (1994)。

井原正隆: "Asymmetric Total Synthesis of Tacamonine(Pseudovincamone I)via Radical Cyclization" J.Org.Chem.59. 5317-5323 (1994)

Masataka Ihara：“通过自由基环化不对称全合成塔卡莫宁（Pseudovincamone I）”J.Org.Chem.59（1994）。