Asymmetric Reactions Utilizing Planar Chiral Transition Metal Complexes

利用平面手性过渡金属配合物的不对称反应

• 批准号: 17550045
• 负责人: UEMURA Motokazu
• 金额: $ 2.3万
• 依托单位: Kyoto Pharmaceutical University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17550045/
• 关键词: arene chromium complex; Fischer carbene complex; planar chirality; axial chirality; asymmetric Heck reaction; Suzuki coupling; フィッシャーカルベン錯体; 不斉Heck反応; Suzukiカップリング; 面不斉アレーン金属錯体; カルベン錯体; 環化反応

We have developed asymmetric reactions by utilizing planar chiral arene transition metal complexes. Prochiral 2,6- dibutenylchrorobenzene chromium complex was subjected intramolecular asymmetric Heck reaction by treatment with chiral palladium(0) catalyst to give optical active indene chromium as planar chiral chromium complex. Furthermore, tandem asymmetric Heck reaction followed by Suzuki-Miyaura cross coupling with arylboronic acid gave optically active indane chromium complex.Binuclear α,β-unsaturated Fischer carbene complexes with planar chiral arene chromium complexes were reacted with alkynes gave optically active cycloheptatriene chromium complexes via [3+2+2]-cycloaddition with high diastereoselectivity.Moreover, binuclear α,β-unsaturated Fischer carbene complexes with planar chiral arene chromium complexes gave α- allyl β-arylpropionates up to 97% ee by reaction with allyl alkoxide and subsequent photo-oxidative demetalation. The chiral hetero-binuclear tungsten carbene compl … More exes afforded anti α-allyl β-hydoxy β-arylpropionates as a major product up to 92/8 dr. The reaction products, α-allyl β-arylpropionates were derived by 1,3-M(CO)_5 shift and subsequent [3,3]-sigmatropic rearrangement.N-Aryl indoles with axially chiral N-C bonds were synthesized by stereoselective nucleophilic substitution reactions of planar chiral arene chromium complexes. Stereoselective chromium tricarbonyl migration was achieved in the sterically hindered N-ary indole chromium complex by refluxing in aromatic solvent.Planar chiral arene chromium complexes with enyne bond were catalyzed by Au(I) catalyst to give axially chiral biaryl chromium complexes by cycloisomerization reactions. The obtained axially chiral biaryl chromium complexes are thermodynamically stable anti-complexes. These anti-biaryl chromium complexes are significant useful, since we have already reported that Suzuki-Miyaura cross coupling of planar chiral aryl bromide chromium complexes with arylboronic acids produced syn-biaryl chromium compresses. Less

我们利用平面手性芳烃过渡金属配合物开发了不对称反应，通过手性钯(0)催化剂处理前手性2,6-二丁烯基氯苯铬配合物进行分子内不对称Heck反应，得到光学活性茚铬平面手性铬配合物。 ，串联不对称 Heck 反应，然后与芳基硼酸进行 Suzuki-Miyaura 交叉偶联，得到光学活性茚满双核α,β-不饱和Fischer卡宾配合物与平面手性芳烃铬配合物与炔烃反应，通过[3+2+2]-环加成反应得到具有高非对映选择性的光学活性环庚三烯铬配合物。此外，双核α,β-不饱和Fischer 卡宾配合物与平面手性芳烃铬配合物产生 α-烯丙基通过与烯丙基醇盐反应和随后的光氧化脱金属作用，β-芳基丙酸酯的产率高达 97%。 8 博士 反应产物α-烯丙基β-芳基丙酸酯衍生自1,3-M(CO)_5位移和随后的[3,3]-σ重排。通过平面手性芳烃铬络合物的立体选择性亲核取代反应合成了具有轴向手性N-C键的N-芳基吲哚，实现了三羰基铬的立体选择性迁移。在芳香族溶剂中回流，形成位阻N-芳基吲哚铬配合物。平面手性具有烯炔键的芳烃铬配合物通过环异构化反应得到轴向手性联芳基铬配合物，所得轴向手性联芳基铬配合物是热力学稳定的反配合物，因为我们发现这些反联芳基铬配合物具有重要意义。已经报道了平面手性芳基溴化物铬配合物的 Suzuki-Miyaura 交叉偶联芳基硼酸产生的顺式联芳基铬压缩物较少。

项目成果

Reaction of α, β-unsaturated Fischer carbene complexes with ally alkoxide

α,β-不饱和费歇尔卡宾配合物与烯丙醇盐的反应

• 发表时间: 2006
• 期刊: Tetrahedron 62
• 作者: K.Kamikawa;A.Tachibana;Y.Shimizu;K.Uchida;M.Furusyo;M.Uemura
• 通讯作者: M.Uemura

遷移金属が配位した面不斉アルデヂド、イミンの還元的カップリングによる光学活性β-ジオール、ジアミン、アミノアルコールの合成

通过平面不对称醛和亚胺与过渡金属配位的还原偶联合成光学活性β-二醇、二胺和氨基醇

• 发表时间: 2006
• 期刊: 有機合成化学協会誌 64
• 作者: 谷口 暢一;多中 良栄;植村 元一
• 通讯作者: 植村 元一

Stereoselective [3+2+2] Cycloaddition Utilizing Optically Active Binuclear Fischer Carbene Complexes with Arene Chromium Complex

利用光学活性双核费歇尔卡宾配合物与芳烃铬配合物进行立体选择性 [3 2 2] 环加成

• 发表时间: 2005
• 期刊: J.Organomet.Chem 690
• 作者: K.Kamikawa;Y.Shimizu;H.Matsuzaka;M.Uemura
• 通讯作者: M.Uemura

「研究成果報告書概要(欧文)」より

摘自《研究结果报告摘要（欧洲）》

• 发表时间: 2006
• 期刊: Seibutsu Butsuri 46(1)
• 作者: Yasushi Shigeri;Keiko Shimamoto
• 通讯作者: Keiko Shimamoto

Stereoselective tricarbonylchromium Migration Reactions in Axially Chiral Biaryl Chromium Complexes

轴向手性联芳基铬配合物中的立体选择性三羰基铬迁移反应

• 发表时间: 2007
• 期刊: J.Organomet. Chem. 692
• 作者: K. Kamikawa;K. Nishino;T. Sakamoto;S. Kinoshita;H. Matsuzaka;M. Uemura;J. Organomet
• 通讯作者: J. Organomet