Development of asymmetric C-H bond activation mediated by new transition metal complexes having a metal centered chirality

具有金属中心手性的新型过渡金属配合物介导的不对称C-H键活化的发展

• 批准号: 15550091
• 负责人: KATAOKA Yasutaka
• 金额: $ 2.37万
• 依托单位: Nara Women's University (2005)Osaka University (2003-2004)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550091/
• 关键词: Cp'-P ligand; rhodium; iridium; π-allyl complex; metal-centered chirality; oxazoline ring; Meerwein reagent; oxidative addition; 珪素-水素結合活性化; ヒドリドシリル錯体; exo型; リニア型; アリル位アルキル化反応; Indox配位子; 光学活性オキサゾリン環; 配位子交換反応

1.We have developed a new method for the construction of a stereogenic center on the metal by the diastereoselective addition of the Meerwein reagent (Me_3OBF_4) to rhodium carbonyl complexes having the Cp'-P ligand, [{3-(R)Ind-P}_<n=2>]H [R = H(a), Et(b), Cy(c), 1'S,2'S,5'R-neomenthyl (NM) (d), 1'R,2'R,5'R-neoisomenthyl (NIM) (e)], in which an indenyl group having a substituent (R) at the 3-position and a diphenylphosphino group are connected by an ethylene group.2.The Index ligands, in which an indenyl group and an oxazoline ring are connected by an ethylene or propylene spacer, have been designed and their iridium(III) and rhodium(III) cationic complexes having a stereogenic center at the metal have been prepared stereoselectively by the ligand exchange reaction of their neutral complexes bearing two prochiral iodido ligands with AgOTf.3.We would like to show the preparation of π-allyl iridium(III) and rhodium(III) complexes having the Cp'-P ligand by using the oxidative addition method. In this case, if a substituent is attached to one of the terminal carbons of the π-allyl ligand, the π-allyl complexes bearing the Cp'-P ligand have a chirality on the metal center. In other words, control of the coordination mode of the p-allyl ligand in the complexes bearing the Cp'-P ligand is the same meaning as control of the stereochemistry around a stereogenic center arising at the metal. Since several substituents are easily introduced at the 3-position of the indenyl group of the Cp'-P ligand, we examined the effect of the substituent to the selectivity of π-allyl complexes. Higher selectivity of the major isomer was obtained when bulkier substituents were introduced at the indenyl group in the Cp'-P ligand.

1.通过Meerwein试剂的非对映选择性加成，我们发展了一种在金属上构建立体中心的新方法（Me_3OBF_4）与具有Cp ′-P配体[{3-（R）Ind-P}_n=2>]H [R = H（a），Et（B），Cy（c），1 ′ S，2 ′ S，5 ′ R-新薄荷基（NM）（d），1 ′ R，2 ′ R，5 ′ R-新异薄荷基（NIM）（e）]，其中在3-位具有取代基（R）的茚基和二苯基膦基通过亚乙基连接。2.索引配体，其中茚基和恶唑啉环通过亚乙基或亚丙基间隔基连接，已经设计了它们的铱（III）和铑（III）通过带有两个前手性碘代配体的中性配合物与AgOTf的配体交换反应，立体选择性地制备了在金属上具有立体中心的阳离子配合物。以显示通过使用氧化加成方法制备具有Cp ′-P配体的π-烯丙基铱（III）和铑（III）络合物。在这种情况下，如果取代基连接到π-烯丙基配体的末端碳之一，则带有Cp '-P配体的π-烯丙基络合物在金属中心上具有手性。换句话说，在带有Cp ′-P配体的络合物中对-烯丙基配体的配位模式的控制与在金属处产生的立体中心周围的立体化学的控制具有相同的含义。由于在Cp '-P配体的茚基的3-位上容易引入几个取代基，我们考察了取代基对π-烯丙基配合物选择性的影响。当在Cp '-P配体的茚基上引入较大的取代基时，主要异构体的选择性更高。

项目成果

Construction of Metal-Centered Chirality : Diastereoselective Addition of the Meerwein Reagent (Me_3OBF_4) to Rhodium Carbonyl Complexes Having the Cp'-P Ligand

金属中心手性的构建：Meerwein 试剂 (Me_3OBF_4) 与具有 Cp-P 配体的羰基铑配合物的非对映选择性加成

• 发表时间: 2004
• 期刊: Organometallicsc 23(9)
• 作者: Kataoka;Yasutaka;Nakagawa;Yousuke;Shibahara;Atsushi;Yamagata;Tsuneaki;Mashima;Kazushi;Tani;Kazuhide
• 通讯作者: Kazuhide

Asymmetric transfer hydrogenation of aryl ketones catalyzed by salt-free two samarium centers supported by a chiral multidentate alkoxy ligand.

• DOI: 10.1002/chin.200515030
• 发表时间: 2004-11
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: K. Ohno;Yasutaka Kataoka;K. Mashima

Yasutaka Kataoka: "Construction of Metal-centered Chirality : Diastereoselective Addition of the Meerwein Reagent (Me_3OBF_4) to Rhodium Carbonyl Complexes Having the Cp'-P Ligand"Organometallics. (in press). (2004)

Yasutaka Kataoka：“金属中心手性的构建：Meerwein 试剂 (Me_3OBF_4) 非对映选择性加成到具有 Cp-P 配体的铑羰基络合物”有机金属化合物。

Rhodium and iridium complexes bearing an alkyloxazoline-substituted indenyl ligand (Indox ligand) and their stereoselective construction of metal-centered chirality

带有烷基恶唑啉取代茚基配体（Indox配体）的铑和铱配合物及其金属中心手性的立体选择性结构

• 发表时间: 2004
• 期刊: Inorganica Chimica Acta 357(10)
• 作者: Kataoka;Yasutaka;Shimada;Koichi;Goi;Takahiro;Yamagata;Tsuneaki;Mashima;Kazushi;Tani;Kazuhide
• 通讯作者: Kazuhide

Rhodium and Iridium Complexes Bearing an Alkyloxazoline-substituted Indenyl Ligand (Indox Ligand) and their Sereoselective Construction of Metal-centered Chiralit

带有烷基恶唑啉取代茚基配体（Indox配体）的铑和铱配合物及其金属中心手性的立体选择性构建

• 发表时间: 2004
• 期刊: Inorg. Chirm. Acta, Topical Volume on Rhodium and Iridium Chemistry 357
• 作者: Yasutaka Kataoka;et al.
• 通讯作者: et al.