New Successive Reactions Utilizing Functional Carbanions

利用功能性碳负离子的新连续反应

• 批准号: 13672217
• 负责人: SHINDO Mitsuru
• 金额: $ 2.62万
• 依托单位: The University of Tokushima
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13672217/
• 关键词: vnolate; cycloaddition; alkene; stereoselective synthesis; tandem reaction; β-lactone enolate; Michael reaction; polvsubstituted carbocycle; アルゲン; イノラートアニオン; オレフィン化反応; カスケード反応; セスキテルペン; 立体電子効果; cucumin E; ベータラクトン

Ynolates are ketene anion equivalens, so that ynolates are converied into reactive species after the first reaction. Using this property, novel successive reactions as well as new synthetic method of ynolates have been developed1. Practical synthetic method of ynolates: Naphithalene catalyzed reductive lithation of dibromo esters leading ynolates was developed.2. Highly Z-selective synthesis of alkenes via tandem [2+2] cycloaddition - ring-opening reaction: Ynolates reacted with acylsilanes to afford polysubstituted vinyl silanes with perfect Z-selectivity. These vinyl silanes produced can be converted into tetrasubstituted alkenes. Ynolates reacted with α-oxyketones to give tetrasubsituted alkenes with high Z-selectivity. These prodeucts were easily converted into butenolides by treatment of acids. This 2-step conversion prosess can be carried out in one-pot.3. Efficient syntheses of carbocycles via tandem [2+2] cycloaddition - Michael reaction: β-Lactone enolates prepared by reaction of ynolates with ketones have high nucleophiliciy. The reaction of ynolates with ketones having an unsaturated eater unit in a proper positionprovided bicyclic β-lactones via tandem [2+2] cycloaddition - Michael addition. The products were easily converted to polysubstituted cycloalkenes in good yield. By this tandem reaction, five-, six- and seven-membered carbocycles can be constructed. Since the products of the tandem reaction are ester enolates, they have uncleophilicity. Taking advantage of this properties, cascade reactions can be carried out to give complex molecules.4. Total synthesis of cucumin E, novel type of triquinane sesquiterpenoid, was achieved using the tandem reaction.

炔醇化物是烯酮阴离子等价物，因此在第一次反应后，醇化物转化为活性物质。利用这一特性，开发了新的连续反应以及新的炔醇化物合成方法1。实用的炔醇化物合成方法：发展了萘催化二溴酯先导炔醇化物的还原锂化反应。 2．通过串联[2+2]环加成-开环反应高度Z选择性合成烯烃：Ynolates与酰基硅烷反应，得到具有完美Z选择性的多取代乙烯基硅烷。这些产生的乙烯基硅烷可以转化为四取代的烯烃。炔化物与α-氧基酮反应生成具有高Z-选择性的四取代烯烃。这些产物很容易通过酸处理转化为丁烯内酯。此两步转化过程可以一锅法进行。3．通过串联[2+2]环加成-迈克尔反应高效合成碳环：由烯醇化物与酮反应制备的β-内酯烯醇化物具有高亲核性。炔醇化物与在适当位置具有不饱和酯单元的酮的反应通过串联[2+2]环加成-迈克尔加成提供双环β-内酯。产物很容易以良好的产率转化为多取代环烯烃。通过这种串联反应，可以构建五元、六元和七元碳环。由于串联反应的产物是酯烯醇化物，因此它们具有亲不亲和性。利用这一特性，可以进行级联反应，得到复杂的分子。4．利用串联反应实现了新型三奎烷倍半萜类化合物黄瓜素 E 的全合成。

项目成果

M.Shindo: "Practical synthesis of ynolate anions: naphthalene-catalyzed reductive lithiation of α, α-dibromoesters"Tetrahedron Letters. 42. 8357-8360 (2001)

M. Shindo：“炔醇阴离子的实用合成：萘催化的 α, α-二溴酯的还原锂化”Tetrahedron Letters 42. 8357-8360 (2001)。

Y.Fukuda: "Diastereoselective Ring Closing Metathesis for the Construction of a Quaternary Carbon Stereogenic Center"Tetrahedron Letters. 43. 2047-2049 (2002)

Y.Fukuda：“用于构建季碳立构中心的非对映选择性闭环复分解”四面体字母。

W.Yokota: "Synthetic studies on Halichlorine and pinnaic acid: palladium mediated construction of the bicyclic spiro core"Heterocycles. 54. 871-885 (2001)

W.Yokota：“卤氯和羽桂酸的合成研究：钯介导的双环螺核心的构建”杂环。

M.Shindo: "Anionic Inverse Electron-Demand 1,3-Dipolar Cycloaddition of Nitrones with Ynolates. Facile Stereoselective Synthesis of 5-Isoxazolidinones Leading to β-Amino Acids"Tetrahedron Letters. 43. 2047-2049 (2002)

M. Shindo：“硝酮与 Ynolate 的阴离子逆电子需求 1,3-偶极环加成。5-异恶唑烷酮的简便立体选择性合成导致 β-氨基酸”Tetrahedron Letters 43。2047-2049 (2002)

M.shindo: "Synthesis of α, α-Dibromo Esters as Precursors of Ynolates"Chem. Pharm. Bull. (印刷中). (2003)

M.shindo：“作为 Ynolates 前体的 α, α-二溴酯的合成”，Chem. Bull (2003)。