Catalytic Asymmetric Synthesis of Chiral Transition-Metal Complexes by the Use of Modern Organic Transformation

利用现代有机转化催化不对称合成手性过渡金属配合物

• 批准号: 24655039
• 负责人: OGASAWARA Masamichi
• 金额: $ 2.66万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Challenging Exploratory Research
• 财政年份: 2012
• 资助国家: 日本
• 起止时间: 2012-04-01 至 2014-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-24655039/
• 关键词: 有機金属化学; 触媒的不斉合成; 均一系触媒; 面不斉; メタロセン; アレーンクロム; メタセシス; 有機合成; 遷移金属錯体; リン原子; 中心不斉; モリブデン; 軸不斉; 金属中心不斉

Kinetic resolution of 1,2-diallylferrocene derivatives by Mo-catalyzed asymmetric ring-closing metathesis (ARCM) gave the corresponding (4,7-dihydroindenyl)iron(II) derivatives in good yields with high enantioselectivity. In the same way, desymmetrization of (1,2,3-triallylindenyl)-metallocenes by ARCM provided the corresponding (1,4-dihydrofluorenyl)-metallocene derivatives in high ee's.The Cs-symmetric zirconocenes could be converted to the corresponding C3-bridged planar-chiral ansa-zirconocenes by ARCM with high enantioselectivity. The obtained planar-chiral ansa-zirconocene complexes could be applicable to the asymmetric carbometallation reaction as catalysts.Kinetic resolution of the racemic planar-chiral (arene)chromium complexes was realized by Mo-catalyzed ARCM with excellent enantioselectivity. The optically active (bromoarene)chromium complex thus obtained is an excellent precursor to various planar-chiral (arene)chromium complexes.

采用钼催化的不对称闭环复分解反应（ARCM）动力学拆分1，2-二烯丙基二茂铁衍生物，得到相应的（4，7-二氢茚基）铁（II）衍生物，收率高，对映选择性好.同样地，（1，2，3-三烯丙基茚基）-茂茂金属的去对称化反应也得到了相应的（1，4-二氢芴基）-茂金属衍生物。Cs-对称的茂锆化合物可以通过ARCM高对映选择性地转化为相应的C3-桥连的平面手性柄型茂锆化合物。所得的平面手性柄型茂锆配合物可作为催化剂应用于不对称碳二亚胺反应，并在钼催化下实现了外消旋平面手性（芳烃）铬配合物的动力学拆分，具有良好的对映选择性.由此获得的光学活性（溴代芳烃）铬络合物是各种平面手性（芳烃）铬络合物的优良前体。

项目成果

Design and Synthesis of Phosphine-Olefin Ligands Having Planar-Chiral (π-Arene)chromium Framework and Application in Asymmetric Catalysis

平面手性(π-芳烃)铬骨架膦-烯烃配体的设计与合成及其在不对称催化中的应用

• 发表时间: 2013
• 作者: Masamichi Ogasawara;Wei-Yi Wu;Takeshi Nakaya;Tomotaka Morita;Sachie Arae;Ya-Yi Tseng;Tamotsu Takahashi;Ken Kamikawa
• 通讯作者: Ken Kamikawa

Enantioselective Morita-Baylis-Hillman Reaction Catalyzed by a Chiral Phosphine Oxide

手性氧化膦催化的对映选择性 Morita-Baylis-Hillman 反应

• DOI: 10.1016/j.tetlet.2013.09.067
• 发表时间: 2013
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: Kotani;S.; Ito;M.; Nozaki;H.; Sugiura;M.; Ogasawara;M.; Nakajima;M.
• 通讯作者: M.

Catalytic Induction of Planar Chirality in Functional Metallocenes by Mo-Catalyzed Asymmetric Ring-Closing Metathesis

Mo催化不对称闭环复分解催化诱导功能茂金属平面手性

• 发表时间: 2013
• 作者: Masamichi Ogasawara;Sachie Arae;Susumu Watanabe;Ayaka Oana;Kiyohiko Nakajima;Tamotsu Takahashi
• 通讯作者: Tamotsu Takahashi

Herically Chiral Dienes in Asymmetric Catalysis : C_2-Symmetric (Z, Z)-1,2-Bis(1-diphenylphosphinylethylidene)cyclo hexanes as Highly Acitve Lewis-Base Organocatalysts

不对称催化中的手性二烯：C_2-对称 (Z, Z)-1,2-双(1-二苯基次膦基亚乙基)环己烷作为高活性路易斯碱有机催化剂

• 发表时间: 2012
• 作者: Ogasawara;M
• 通讯作者: M

Catalytic Enantioselective Synthesis of Axially Chiral N-Aryl Indole Chromium Complex by Molybdenum-Catalyzed Asymmetric Desymmetrization

钼催化不对称去对称催化对映选择性合成轴向手性N-芳基吲哚铬络合物

• 发表时间: 2012
• 作者: Ken Kamikawa;Sachie Arae;Wei-Yi Wu;Chihiro Nakamura;Tamotsu Takahashi;Masamichi Ogasawara
• 通讯作者: Masamichi Ogasawara