Search for Asymmetric Catalytic Reactions using Low-valent Zirconium Complex

使用低价锆配合物寻找不对称催化反应

• 批准号: 08672447
• 负责人: HANZAWA Yuji
• 金额: $ 1.41万
• 依托单位: School of Pharmacy, Tokyo University of Pharmacy and Life Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08672447/
• 关键词: Early transition metal; Zirconocene-butene complex; Catalytic reaction; Diastereoselective synthesis; Regioselective reaction; Asymmetric synthesis; ハイドロジルコネーション; ジルコノセン-(1-ブテン)錯体; エポキシオレフィン; 不斉触媒反応; 環変換反応; Schwartz試薬; ビニルエポキシド; ビニルシクロアルカン

In our ongoing research project on asymmetric catalytic reactions using low-valent zirconocene complex, we have exploited enormous possibilities of low-valent zirconium complex, zirconocene-butene complex, for organic synthesis. During the past term of the project we established several new zirconocene-butene complex-mediated synthetic procedures which must be elaborated to be catalytic and asymmetric. At present we could developed a new zirconocene-butene complex catalyzed ring opening reactions of vinyl cyclopropane derivatives whose stoichiometric reactions have been applied to stereocontrolled syntheses of steroidal side chains. Although the asymmetric version of these reaction has not been succeeded yet, we are currently continueing the research to find the most effective chiral ligand for zirconium metal complex.

在我们正在进行的利用低价茂锆络合物进行不对称催化反应的研究项目中，我们开发了低价锆络合物--茂锆丁烯络合物用于有机合成的巨大可能性。在过去的项目期间，我们建立了几个新的新的茂锆丁烯络合物介导的合成方法，这些方法必须详细说明是催化的和不对称的。目前，我们已开发出一种新型的茂锆丁烯络合物催化的乙烯基环丙烷衍生物的开环反应，其化学计量反应已应用于立体控制的甾体侧链的合成。虽然这些反应的不对称版本还没有成功，但我们目前正在继续研究，寻找对锆金属络合物最有效的手性配体。

项目成果

Hanazawa Y.: "Regioselective Bond Cleavage of Vinylcyclopropane Derivatives with the Zirconocene-Butene Complex" Tetrahedron Lett.35. 9421-9424 (1994)

Hanazawa Y.：“乙烯基环丙烷衍生物与二茂锆-丁烯复合物的区域选择性键断裂”四面体 Lett.35。

Harada, S.: "Complexation of Uinylcyclopropanes with Zirconocene-butene complex" J.Org.Chem.38. 3994-4001 (1997)

Harada, S.：“乙烯基环丙烷与二茂锆-丁烯络合物的络合”J.Org.Chem.38。

Harada, S.: "Formation of Cyclopropyl Carbinols Through a Highly Diastereoselective Hydrozirconation of Vinyloxirane Derivatives" Tetrahedron Lett.38. 1957-1960 (1997)

Harada, S.：“通过乙烯基环氧乙烷衍生物的高度非对映选择性氢化锆化形成环丙基甲醇”Tetrahedron Lett.38。

Hanzawa, Y.: "New "Cp_2Zr" -mediated Ring Transformations of 2-Vinyl-heterocycles to Carbocycles" Tetrahedron Lett.38. 4615-4618 (1997)

Hanzawa, Y.：“新的“Cp_2Zr”介导的 2-乙烯基杂环到碳环的环转化”四面体 Lett.38。

Harada S.: "Complexation of Vinylcyclopropanes with Zirconocene-1-butene Complex : Application to the Stereocontrolled Synthesis of Steroidal Side Chains" J.Org.Chem.62. 3994-4001 (1997)

Harada S.：“乙烯基环丙烷与二茂锆-1-丁烯络合物的络合：在甾体侧链立体控制合成中的应用”J.Org.Chem.62。