Synthesis and Development of Novel Main Group Element Compounds having Tin-based Steric Protection Group

具有锡基空间保护基团的新型主族元素化合物的合成与开发

• 批准号: 16550043
• 负责人: MINOURA Mao
• 金额: $ 2.37万
• 依托单位: Kitasato University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550043/
• 关键词: Main group element; Steric Protection; Crystallography; Tin; Sulfur; 結晶構造; 動的挙動; トリプチセン; 立体化学

In recent years there has been much interest in the reactive main group element compounds having an efficient steric protection group because of their unique chemical properties. Although many successes and developments of the steric protection groups have been reported, the central atom has been limited to carbon in many cases. In this research project, we have been investigating on the tin-based steric protection groups for the kinetic stabilization of reactive functional groups. For example, tris(9-triptycyl)stannyl group (Trp_3Sn-) has been shown as an effective steric protection group for-SOH function. Also, we synthesized and investigated on the related compounds bearing three 9,10-dihydro-9,10-ethenoanthracen-l-yl (Dbb) groups on a central tin atom (Dbb_3Sn-) as a novel tin-based steric protection group. Also, the synthesis and functionalization of methylbis(9-triptycyl)stannyl group (Trp_2MeSn-) has been studied.Moreover, static and dynamic stereochemistry of several Trp3Sn-compounds were studied. X-ray crystallography of the Trp3SnX (X= hologenes, alkyl groups) showed that the three Trp goups meshed with each other like bevel gears and formed near-C3 chiral conformation. In solution, the process of enantiomerization of those Trp3SnX compounds has been investigated by VT-NMR method.

近年来，具有有效空间位阻保护基团的反应性主族元素化合物由于其独特的化学性质而引起人们极大的兴趣。虽然已经报道了空间保护基团的许多成功和发展，但在许多情况下中心原子仅限于碳。在本研究计划中，我们一直在研究锡基空间位阻保护基团对反应性官能团的动力学稳定作用。例如，三（9-三蝶基）甲锡烷基（Trp_3Sn-）已被证明是-SOH功能的有效空间保护基团。此外，我们还合成并研究了中心锡原子（Dbb_3Sn-）上带有三个9，10-二氢-9，10-乙烯基蒽基（Dbb）的相关化合物，作为一种新型的锡基空间位阻保护基团。研究了甲基双（9-三蝶基）锡基（Trp_2MeSn-）的合成和功能化，并对几种Trp_3Sn-化合物的静态和动态立体化学进行了研究。X-射线衍射分析表明，Trp 3SnX（X= hologenes，烷基）的三个Trp基团以锥齿轮的形式相互啮合，形成近C3手性构象。用VT-NMR方法研究了Trp 3SnX化合物在溶液中的对映异构化过程。

项目成果

Synthesis and Stereochemistry of N-Phenyl-N-9-triptycylhydroxylamine Derivatives and Related Compounds

• DOI: 10.1246/bcsj.77.2273
• 发表时间: 2004-12
• 期刊: Bulletin of the Chemical Society of Japan
• 影响因子: 4
• 作者: Chiharu Agawa;Keiko Otsuka;M. Minoura;Y. Mazaki;G. Yamamoto

Static and Dynamic Stereochemistry of Tris(9-triptycyl) stannane Derivatives

三(9-三蝶基)锡烷衍生物的静态和动态立体化学

• 发表时间: 2005
• 期刊: Bull. Chem. Soc. Jpn. 78・3
• 作者: A.F.M.Mustafizur Rahman;T.Murafuji;K.Kurotobi;Y.Sugihara;N.Azuma;A.F.M.Musutafizur Rahman 他;A.F.M.Musutafizur Rahman 他;Gaku Yamamoto
• 通讯作者: Gaku Yamamoto

Static and Dynamic Stereochemistry of Tris (9-triptycyl) stannane Derivatives

Tris (9-triptycyl) 锡烷衍生物的静态和动态立体化学

• 发表时间: 2005
• 期刊: Bull.Chem.Soc.Jpn. 78-3
• 作者: A.F.M.Mustafizur Rahman;T.Murafuji;K.Kurotobi;Y.Sugihara;N.Azuma;A.F.M.Musutafizur Rahman 他;A.F.M.Musutafizur Rahman 他;Gaku Yamamoto;Gaku Yamamoto
• 通讯作者: Gaku Yamamoto

Static and Dynamic Stereochemistry of Tris(9-triptycyl)stannane Derivatives

三(9-三蝶基)锡烷衍生物的静态和动态立体化学

• 发表时间: 2005
• 期刊: Bull.Chem.Soc.Jpn. 78・3
• 作者: A.F.M.Mustafizur Rahman;T.Murafuji;K.Kurotobi;Y.Sugihara;N.Azuma;A.F.M.Musutafizur Rahman 他;A.F.M.Musutafizur Rahman 他;Gaku Yamamoto;Gaku Yamamoto;Gaku Yamamoto
• 通讯作者: Gaku Yamamoto