Development of novel addition reactions based on the key concept of carbon-metal-hetero atom bonds

基于碳-金属-杂原子键关键概念的新型加成反应的发展

• 批准号: 14550817
• 负责人: FUGAMI Keigo
• 金额: $ 1.98万
• 依托单位: Gunma University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550817/
• 关键词: Organotin Reagent; Organogermanium Reagent; Palladium Catalyst; Addition Reaction; Mizoroki-Heck Reaction; Carbostannylation Reaction; Hyoer-Valent Tin Compound; Heteroatom Compound; 有機ゲルマニウム; クロスカップリング反応; 有機スズ; ハロゲン化物; 熱分解; アルケニルゲルマン; 置換反応

The reporter has focused on compounds that possess carbon-tin-hetero atom-or carbon-germanium-heteroatom bonds from synthetic point of view. On the investigation, it was revealed that Lewis acidity tin and germanium with those bonds are enhanced. It resulted in discoveries of new aspects in organotin-and germanium chemistries as follows : 1.oxidative addition to palladium(0) species is facilitated ; 2.due to the enhancement of Lewis acidity of the resulting adduct realized otherwise sluggish carbopalladation process ; 3.tend to form a hyper-valent species, nucleophilicity of the carbon groups attached on tin or germanium are significantly enhanced upon addition of a proper anionic ligand.Based on above mentioned discoveries, several synthetically useful new carbon-carbon bond-formation reactions could be developed. Especially, achievement of utilization of plural organic moieties attached to tin or germanium toward the cross-coupling reactions, that had been widely regarded practically impossible, is noteworthy.The newly developed synthetic organic reactions are listed below :1.Tetraaryltin-mediated novel Mizoroki-Heck-type reaction utilizing plural organic moieties attached to a tin atom.2.Palladium-catalyzed cross-coupling reaction of tetraaryl-and -alkenyltin reagents that utilizes all four organo groups on tin.3.Arylstannylation of norbornene.4.Allylstannylation of norbornene.5.Palladium-catalyzed oxidative 2;1 cyclocondensation of norbornene and 1-alkenyltin trichloride.6.Aryltin trichloride-mediated Mizoroki-Heck reaction that does not require added oxidant.7.Alkynylgermylation of norbornene and its derivatives.8.New stereoselective synthesis of Z-enynylgermanium trichloride by means of thermal cracking of alkynylgermylated norbornadiene.9.Novel palladium-catalyzed cross-coupling reaction of arylgermanium trichlorides.

记者从合成的角度重点关注了具有碳-锡-杂原子-或碳-锗-杂原子键的化合物。调查发现，锡和锗与这些键的路易斯酸性增强。它导致了有机锡和锗化学的新方面的发现，如下： 1.促进了钯(0)物质的氧化加成； 2.由于所得加合物的路易斯酸性增强，实现了原本缓慢的碳钯化过程； 3.倾向于形成超价物质，添加适当的阴离子配体后，锡或锗上附着的碳基团的亲核性显着增强。基于上述发现，一些合成上有用的新碳-碳键形成反应可以得到开发。尤其值得注意的是，利用锡或锗上连接的多个有机部分进行交叉偶联反应，这曾被广泛认为实际上是不可能的。新开发的有机合成反应如下：1.四芳基锡介导的新型Mizoroki-利用连接到锡原子的多个有机部分的 Heck 型反应。2.四芳基-和-烯基锡试剂的钯催化交叉偶联反应，利用锡上的所有四个有机基团。3.降冰片烯的芳基甲锡烷基化。4.降冰片烯的烯丙基甲锡烷基化。5.钯催化的降冰片烯和三氯化 1-链烯基锡的氧化 2;1 环缩合反应。6.三氯化芳基锡介导的 Mizoroki-Heck 反应，需要添加氧化剂。7.降冰片烯及其衍生物的炔基甲酰化。8.新炔基甲酰化降冰片二烯热裂解立体选择性合成Z-烯炔基三氯化锗。9.新型钯催化三氯化芳基锗交叉偶联反应。

项目成果

Keigo Fugami: "Palladium-catalyzed novel addition-elimination reaction of alkenyltin reagents to norbornene"Journal of Organometallic Chemistry. 687・2. 567-569 (2003)

Keigo Fugami：“钯催化的烯基锡试剂与降冰片烯的新型加成消除反应”有机金属化学杂志 687・2（2003）。

Palladium-catalyzed cross-coupling reaction by means of organogermanium trichlorides

• DOI: 10.1002/adsc.200404187
• 发表时间: 2004-12-01
• 期刊: ADVANCED SYNTHESIS & CATALYSIS
• 影响因子: 5.4
• 作者: Enokido, T;Fugami, K;Kosugi, M
• 通讯作者: Kosugi, M

M.Kosugi, K Fugami: "A Historical Note of the Stille Reaction"J. Organomet. Chem.. 653巻・1-2号. 50-53 (2002)

M.Kosugi，K Fugami：“Stille 反应的历史记录”J. 化学杂志，第 653 卷，第 50-53 期（2002 年）。

A historical note of the Stille reaction

• DOI: 10.1016/s0022-328x(02)01270-6
• 发表时间: 2002-07-01
• 期刊: JOURNAL OF ORGANOMETALLIC CHEMISTRY
• 影响因子: 2.3
• 作者: Kosugi, M;Fugami, K
• 通讯作者: Fugami, K

Novel synthetic organic reactions of organotin reagents based on tin-hetero atom bond

基于锡-杂原子键的有机锡试剂新型有机合成反应

• 发表时间: 2003
• 期刊: Yuki Gosei Kagaku Kyokaishi 61
• 作者: K Fugami;M.Kameyama;M.Kosugi
• 通讯作者: M.Kosugi