Development of Novel Catalytic systems Using by the Cp'-P Ligand Having a Planar Chirality

利用具有平面手性的 Cp-P 配体开发新型催化系统

• 批准号: 11650894
• 负责人: KATAOKA Yasutaka
• 金额: $ 2.18万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650894/
• 关键词: Cp'-P ligand; planar chirality; stereogenic center; chirality on Rh center; migration; retro-migratoryinsertion; acylmethylation; stereoselective; アミノアルコール; ジイン誘導体; メチルアシル化反応; イミン; ロジウム; ジヒドロフラン; アルデヒド; ノルボルネン; イシン; 立体特異的; 金属上の不斉; アルキン

I have been working on chemistry of transition metal complexes having the Cp'-P ligand. The Cp'-P ligand has both a cyclopentadienyl derivatives and a tertiary phosphine group connected by an appropriate spacer. The complexes having Cp'-P ligand are expected to show the combination character of cyclopentadienyl complexes and phosphino complexes. Addition of them, we can disclose an interesting behavior of the Cp'-P ligand through our research.In this project, I can find some interesting results obtained by using the Cp'-P ligand. Main points are shown the followings.First, I have prepared the several kinds of Cp'-P ligand and examined their characters. We can find out that the combination of planar chirality and stereogenic center on the substituent was very effective for controlling the chirality on Rh center.Second, we have obtain experimental evidence for migration of an alkyl group in migratory insertion and retro-Migratory Insertion by using the three-legged piano-stool rhodium Complex having Cp'-P Ligand.Third, as an application to organic synthesis, I have developed stereo- and regio selective acylmethylation of alkynes mediated by the Cp'-P Rh complexes.

我一直在研究具有Cp'-P配体的过渡金属配合物的化学。Cp′-P配体既有环戊二烯基衍生物，又有叔膦基，由适当的间隔剂连接。具有Cp′-P配体的配合物具有环戊二烯基配合物和磷酸配合物的结合特性。加上它们，我们可以通过我们的研究揭示Cp'-P配体的一个有趣的行为。在这个项目中，我发现使用Cp'-P配体得到了一些有趣的结果。要点如下。首先，制备了几种Cp'-P配体，并对其性质进行了研究。我们发现，平面手性和取代基上的立体中心的结合对于控制Rh中心的手性是非常有效的。其次，我们利用具有Cp′-P配体的三足钢琴凳铑配合物获得了烷基在迁移插入和反迁移插入中的迁移的实验证据。第三，作为有机合成的应用，我已经开发了由Cp'- p Rh配合物介导的炔的立体和区域选择性酰基甲基化。

项目成果

Yasutaka kataoka et al.: "Stereospecific CO Insertion into the Rh-Methyl s-bond in [(Cp'-P)Rh(CO)(Me)]BF_4 and Deinsertion from [(Cp'-P)Rh(COMe)I] : Experimental Evidences for Methyl Migration"Organometallics. 20巻. 2431-2433 (2001)

Yasutaka kataoka 等人：“立体特异性 CO 插入 [(Cp-P)Rh(CO)(Me)]BF_4 中的 Rh-甲基 s-键并从 [(Cp-P)Rh(COMe)I 中脱嵌” ]：《甲基迁移的实验证据》《有机金属学》。第 20 卷。2431-2433 (2001)

Yasutaka kataoka et al.: "Configurationally Stable Metal-centered Chirality : Stereospecific and Regioselective Rhodaacylation of Alkynes Controlled by the Third Generation of the [Cp'-P]H Ligand"Chem. Commun.. 841-842

Yasutaka kataoka 等人：“构型稳定的金属中心手性：第三代 [Cp-P]H 配体控制的炔烃的立体特异性和区域选择性 Rhodaacylation”Chem.

Yasutaka Kataoka, Atsushi Shibahara, Tsuneaki Yamaeata and Kazuhide Tani: "Configurationally Stable Metal -centered Chirality: Stereospecific and Regioselective Rhodaacylation of Alkynes Controlled by the Third Generation of the [Cp'-P]H Ligand"Chem. Comm

Yasutaka Kataoka、Atsushi Shibahara、Tsuneaki Yamaeata 和 Kazuhide Tani：“构型稳定的金属中心手性：由第三代 [Cp-P]H 配体控制的炔烃的立体特异性和区域选择性 Rhodaacylation”Chem。

片岡靖隆: "Configurationally Stable Metal-Centered Chirality Stereospecific and Regroselective Rhodacylation of Alkynes."Chem.Commun.. 841-842 (2000)

Yasutaka Kataoka：“炔烃的构型稳定的金属中心手性立体定向和再选择性罗达酰化。”Chem.Commun.. 841-842 (2000)

Yasutaka Kataoka, Yoko Iwato, Tsuneaki Yamagata, and Kazuhide Tani: "The Third Generation of the Cp'-P Ligand: Highly Stereoselective Control of Central Chirality Arising at a Metal Center"Organometallics. 18. 5423-5425 (1999)

Yasutaka Kataoka、Yoko Iwato、Tsuneaki Yamagata 和 Kazuhide Tani：“第三代 Cp-P 配体：金属中心产生的中心手性的高度立体选择性控制”有机金属学。