Development of New Synthetic Methods based on Early Transition Metals

基于早期过渡金属的新合成方法的开发

• 批准号: 05671770
• 负责人: HANZAWA Yuji
• 金额: $ 1.34万
• 依托单位: Tokyo College of Pharmacy
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05671770/
• 关键词: Early transition metal; Zirconocene-butene complex; Ring contraction; Steroidal side chains; Diastereoselective synthesis; Catalyst; Oxetanocin; Vinylcyclopropane; ジルコノセン-ブテン錯体; η^3-πアリルジルコノセン錯体; ステロイド; ジルコノセン等価体; アリルジルコニウム; 環縮小反応; ビニルモルホリン

In our ongoing research project on organic syntheses using early transtition metals, zirconium, vanadium, niobium etc., we have exploited enormous possibilities of low valent zirconium complex, zirconocene-butene complex, for organic synthesis. During the past term of project we established an efficient method for the preparation of optically pure carbocycles by treating vinyl sugar derivatives with zirconocene-butene complex and an application to the synthesis of bioactive molecules. We also established the construction of steroidal side chain based on the reaction of zirconocene with vinylcyclopropane, and we have also studied a short-step construction of steroidal skeleton based on the reaction of zirconocene and alkoxymethylated stirene derivatives.

在我们正在进行的使用早期过渡金属、锆、钒、铌等有机合成的研究项目中，我们开发了低价锆络合物、二茂锆-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，我们建立了一种通过用二茂锆-丁烯络合物处理乙烯基糖衍生物来制备光学纯碳环的有效方法，并将其应用于生物活性分子的合成。我们还建立了基于二茂锆与乙烯基环丙烷反应的甾体侧链的构建，并研究了基于二茂锆与烷氧基甲基化苯乙烯衍生物反应的甾体骨架的短步构建。

项目成果

Ito, H.: "Ziconium-mediated highly diastereoselective ring contraction of carbohydrate derivatives : Synthesis of highly functionalized, enantiomerically pure carbohydarte." J.Am. Chem. Soc.115 (19). 8835-8836 (1993)

Ito, H.：“锆介导的碳水化合物衍生物的高度非对映选择性环收缩：高度功能化、对映体纯的碳水化合物的合成。”

Yuji Hanzawa: "Regioselective Bond Cleavage of Vinylcyclopropane Derivatives with the Ziroonocene-Butene Complex" Tetrahedron Lett.35. 9421-9424 (1994)

Yuji Hanzawa：“乙烯基环丙烷衍生物与锆茂丁烯复合物的区域选择性键断裂”Tetrahedron Lett.35。

Ito, H.: "Practical zirconium-mediated deprotective method of allyl groups." J.Org. Chem.58 (3). 774-775 (1993)

Ito, H.：“实用的锆介导的烯丙基脱保护方法。”

ITO, HISANAKA: "Generation of allglic and relateol organozirconiums through a highly effective zirconium-β-alkoxide elimination" Tetrahedron. 51. 4507-4518 (1995)

ITO, HISANAKA：“通过高效消除锆-β-醇盐生成所有有机锆”Tetrahedron 51. 4507-4518 (1995)。

Hisanaka Ito: "Ziroonium mediated,Highly Diastereoselective Ring Contraction of Vinylmorpholine Derivatives from Amino Acid" J.Am.Chem.Soc. 116. 5469-5470 (1994)

Hisanaka Ito：“锆介导的氨基酸乙烯基吗啉衍生物的高度非对映选择性环收缩”J.Am.Chem.Soc。