Research for Asymmetric Synthesis of Group 14-Element Centered Anions

14族中心阴离子的不对称合成研究

• 批准号: 18550044
• 负责人: NANJO Masato
• 金额: $ 2.68万
• 依托单位: Tottori University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550044/
• 关键词: germvllithium; silvllithium; stannvllithium; optically active; absolute structure; asymmetric synthesis; 溶媒効果; 立体安定性; 絶対構造

Optically active organic germanium compounds bearing asymmetric germanium atom (methyl-1-naphtylphenylgermane and its derivatives) was previously reported by Brook et.al. However, far less attention has been devoted to optically active germyllithium or stannyllithium species. We report herein the results of a study of novel optically active germyllithium, using (-)-sparteine as a chiral ligand.In the Schlenk tube, tert-butylmethylphenylgermyllithium (t-BuMePhGeLi) (1) was prepared by the reaction of the corresponding hydrogermane with tert-butyllithium in THF in the presence of half amounts of (-)-sparteine. The compound of 1 was characterized by ^1H, ^7Li and ^13C NMR spectra. The ligand-exchange reaction between 1-(sp) and 1-(THF)_2 was observed by variable-temperature NMR spectroscopy. The coalescence point was 107℃, and free energy of activation was calculated to be 18.0 kcal/mol. Optical resolution of germyllithium with (-)sparteine (1^*) was succeeded by recrystallization from n- … More hexane / toluene mixed solvent. The molecular structure of 1^* was determined by X-ray diffraction. As a result, absolute configuration of optically active 1^* was R configuration.This method could also be applied to synthesis of optically active stannyllithium. Optical resolution of stannyllithium was succeeded by only addtion of half amount of (-)-sparteine into the racemic mixture of tert-butylmethylphenylstannyllithium (t-BuMePhSnLi) (2). The optically pure stannyllithium (-)-sparteine complex 2-(sp) was obtained as colorless crystals and its absolute structure had R configuration determined by X-ray crystallography.In the presence of (-)-sparteine, tert-butylmethylgermane (t-BuMeGeH_2) was reacted with sec-butyllithium to give a (-)-sparteine complex of tert-butylmethylhydrogermyllithium (t-BuMeHGeLi, 3), quantitatively. 3-(sp) was added to triphenylchlorosilane to yield a coupling product of tert-butylmethyl (triphenylsilyll germane (t-BuMeHGeSiPh_3). The resulting optically active silylgermane shows 48%ee, and the absolute structure of the main product was determined by a single crystal X-ray diffraction to be S configuration. Less

Brook等人先前报道了带有不对称锗原子的光学活性有机锗化合物（甲基-1-萘基苯基锗烷及其衍生物）。然而，对光学活性的甲锂或甲锡锂物种的关注却少之又少。我们在此报告了使用 (-)-金雀花石作为手性配体的新型光学活性锗基锂的研究结果。在 Schlenk 管中，通过相应的氢锗烷与叔丁基锂在 THF 中在一半量的 (-)-金雀花石存在下反应制备了叔丁基甲基苯基甲锗基锂 (t-BuMePhGeLi) (1)。 1的化合物通过 1H、 7Li 和 13C NMR谱进行表征。通过变温核磁共振波谱观察1-(sp)和1-(THF)_2之间的配体交换反应。聚结点为107℃，计算活化自由能为18.0 kcal/mol。通过从正己烷/甲苯混合溶剂中重结晶，成功地用(-)金雀花石 (1^*) 光学拆分了甲锂。通过X射线衍射测定了1^*的分子结构。结果表明，光学活性1^*的绝对构型为R构型。该方法也可应用于光学活性锡锂的合成。只需将一半量的 (-)-金豆石碱添加到叔丁基甲基苯基甲锡基锂 (t-BuMePhSnLi) 的外消旋混合物中即可成功实现甲锡锂的光学拆分 (2)。得到光学纯的甲锡锂配合物2-(sp)，为无色晶体，通过X射线晶体学测定其绝对结构为R构型。在(-)-金雀花碱存在下，叔丁基甲基锗烷(t-BuMeGeH_2)与仲丁基锂反应，得到(-)-金雀花石配合物 叔丁基甲基氢甲锂（t-BuMeHGeLi，3），定量。将3-(sp)加入到三苯基氯硅烷中，得到叔丁基甲基(三苯基甲硅烷基锗烷(t-BuMeHGeSiPh_3))的偶联产物。所得光学活性甲硅烷基锗烷的ee值为48%，经单晶X射线衍射测定主产物的绝对结构为S构型。

项目成果

Thermal Reactivity of cis- and trans-Bis(triphenylgermyl)bis(tertiaryphosphine)- platinum (II)

顺式和反式双(三苯基甲锗烷基)双(叔膦)-铂(II)的热反应性

• 发表时间: 2007
• 期刊: Journal of Organometallic Chemistry 692
• 作者: Kunio;Mochida;Takashi;Fukushima;Michiko;Suzuki;Wakako;Hatanaka;Mariko;Takayama;Yoko;Usui;Masato;Nanio;Kuniyoshi;Akasaka;Takako;Kudo;Sanshiro;Komiya
• 通讯作者: Komiya

Reactions of a Zerovalent Platinum Complex with 1,2-Dihydrodisilane.

零价铂络合物与 1,2-二氢二硅烷的反应。

• 发表时间: 2006
• 作者: Yoshiyuki;Miura;Kanako;Ito;Seigo;Ohta;Keiko;Yano;Masato;Nanjo;Yoko;Usui;Kunio;Mochida;Masato Nanjo;南条 真佐人;南条 真佐人
• 通讯作者: 南条 真佐人

Preparation, Structural Characterization, and Photochemical Reactions of Silyl-and Germylborates.

甲硅烷基硼酸盐和甲硼酸硼酸盐的制备、结构表征和光化学反应。

• 发表时间: 2006
• 期刊: Organometallics 25
• 作者: Kunio;Mochida;Takashi;Fukushima;Michiko;Suzuki;Wakako;Hatanaka;Mariko;Takayama;Yoko;Usui;Masato;Nanio;Kuniyoshi;Akasaka;Takako;Kudo;Sanshiro;Komiya;Kunio Mochida;Masato Nanjo
• 通讯作者: Masato Nanjo

Thermal Reactivity of cis-and trans-Bis(triphenylgermyl)bis(tertiaryphosphine)-platinum(II)

顺式和反式双(三苯基甲锗烷基)双(叔膦)-铂(II)的热反应性

• 发表时间: 2007
• 期刊: Journal of Organometallic Chemistry 692
• 作者: Kunio;Mochida;Takashi;Fukushima;Michiko;Suzuki;Wakako;Hatanaka;Mariko;Takayama;Yoko;Usui;Masato;Nanio;Kuniyoshi;Akasaka;Takako;Kudo;Sanshiro;Komiya;Kunio Mochida
• 通讯作者: Kunio Mochida

Synthesis of New Self-assembled Octahedrons Containing Group 14 Elements Dative Bonding of Pyrimidine Derivatives with Palladium Ions

嘧啶衍生物与钯离子配位键合成含14族元素的新型自组装八面体

• 发表时间: 2006
• 期刊: Organometallics 25
• 作者: Masato;Kazuhiko;Matsudo;Mari;Kurihara;Sayaka;Nakamura;Yoshio;Sakaguchi;Hisaharu;Hayashi;Kunio;Mochida
• 通讯作者: Mochida