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

我们通过使用平面性芳烃过渡金属复合物发展了不对称反应。 2,6-二丁基苯基苯基铬铬复合物通过用手性钯（0）催化剂处理将光学活性indene铬作为平面性手chiral铬复合物处理，以分子内不对称的HECK反应。此外，串联不对称的heck反应，然后与芳基硼酸交叉耦合，从而产生了光学活跃的甘烷基铬复合物。双核α，β-β-饱和的fischer碳纤维碳烯配合物通过平面芳香族芳烃复合物与烯烃复合物与烯烃复合物相应，使其与烯烃复合物反应。 [3+2+2] - 具有高映射性的环载条件。此外，双核α，β-不饱和的fischer碳碳碳纤维复合物与平面性手性芳烃铬配合物可通过与Allyl Alkoxient and sefatextabity Dexetal and toxex todectal and coptation coppation抗反应，可提供α-烯丙基β-β-芳基磷酸盐。手性杂质 - 二核钨碳酸碳纤维comp…更多的EXE提供了抗α-酰胺β-羟基β-羟基丙酸酯作为主要产物，最高为92/8 DR。反应产物通过1,3-m（CO）_5移动和随后的[3,3] - 含量重排。N-芳基芳烃固定剂通过敏感性的N-C键通过刻板性的核铬铬合成。立体选择性铬铬迁移是通过在芳族溶液中回流的立体限制的N- ARY吲哚铬复合物中实现的。 Au（i）催化剂催化具有Enyne键的平面性手性芳烃复合物，通过环状反应反应给出轴向手性的Biaryl Chromium Chormium铬配合物。获得的轴向手性双铬复合物是热力学稳定的抗复合物。这些抗生物L铬复合物具有很大的有用，因为我们已经报道了铃木 - 米约拉拉与芳基硼酸产生的syn-biaryl铬压缩的平面性手性芳基溴化溴化物铬复合物的交叉耦合。较少的

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