Catalytic Asymmetric Hydrogenation of Ketones Using non-Phosphine-Based N4 Ligands

使用非膦基 N4 配体催化酮的不对称氢化

• 批准号: 21350053
• 负责人: KITAMURA Masato
• 金额: $ 12.31万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2009
• 资助国家: 日本
• 起止时间: 2009 至 2011
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-21350053/
• 关键词: 不斉合成; 機構解明; 窒素系配位子; Ph-BINAN-H-Py; ルテニウム; 不斉水素化; 反応機構

Homogeneous asymmetric hydrogenation of ketones using chiral diphosphine-Ru(II) complexes has been established as one of the most reliable strategies for the synthesis of optically active secondary alcohols since our Ru(OCOCH-3)-2(binap)/HCl combined catalyst made its debut in 1987. Having apparently started a trend with BINAP. Ru systems, a tremendous number of hydrogenation-active Ru complexes with trivalent phosphorus ligating atoms have been reported. The effectiveness has been examined and compared with the" privileged" BINAP system and its derivatives. In comparison, asymmetric hydrogenation using non-phosphine-based Ru complexes is still in the developmental stage. We have designed and synthesized Ph-BINAN-H-Py(3, 3'-Ph, Ph-N2, N2'-bis(pyridin-2-ylmethyl)-1, 1'-binaphthyl-2, 2'-diamine) which is characterized by a) inside sp^3N/outside sp^2N, b) donor-acceptor bifunctional ability, and c) cis-alpha-selective formation of octahedral metal complexes. The utility of ligands has been demonstrated in asymmetric hydrogenation of aromatic ketones in combination with a Ru-π-allyl precursor. The reaction quantitatively proceeds with the S/C ratio of over 10, 000 with up to 99 : 1 enantioselectivity. The success using non-phosphine ligand has made a new trail to asymmetric hydrogenation chemistry.

自从我们的RU（OCOCH-3）-2（BINAP）/HCL组合催化剂在1987年首次亮相以来，使用手性二磷蛋白RU（II）复合物对酮的均质不对称氢化已被确定为合成光学活性次级酒精的最可靠的策略之一。据报道，RU系统是大量氢化活性RU复合物，具有三价磷结扎原子。已经检查了有效性，并将其与“特权” BINAP系统及其衍生物进行了比较。相比之下，使用基于非膦的RU复合物的不对称氢化仍处于发育阶段。 We have designed and synthesized Ph-BINAN-H-Py(3, 3'-Ph, Ph-N2, N2'-bis(pyridin-2-ylmethyl)-1, 1'-binaphthyl-2, 2'-diamine) which is characterized by a) inside sp^3N/outside sp^2N, b) donor-acceptor bifunctional ability, and c) cis-alpha-selective formation of octahedral metal complexes.配体的效用已在芳族酮的不对称氢与RU-π-酰基前体结合使用。该反应以超过10,000的S/C比进行定量进行，最高为99：1对映选择性。使用非磷酸配体的成功已为非对称氢化化学的新轨迹开辟了道路。

项目成果

Asymmetric Dehydrative Cyclization of ω-Hydroxy Allyl Alcohols Catalyzed by Ruthenium Complexes

• DOI: 10.1002/anie.200904671
• 发表时间: 2009-01-01
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Tanaka, Shinji;Seki, Tomoaki;Kitamura, Masato
• 通讯作者: Kitamura, Masato

Metathesis-type Donor-Acceptor Bifunctional Catalyst(DACat) and Redox-type DACat

复分解型供体-受体双功能催化剂(DACat)和氧化还原型DACat

• 发表时间: 2011
• 作者: 平尾明;渡部拓海;H-S. Yoo;M. Kitamura
• 通讯作者: M. Kitamura

アリル化合物類の製造方法

烯丙基化合物的制造方法

• 发表时间: 2010

2-アルケニルアミン化合物の製造方法

2-烯基胺化合物的制造方法

• 发表时间: 2011

Fe_3O_4@SiO_2-L-CpRu : A Magnetically Separable Heterogeneous Deallylation Catalyst

Fe_3O_4@SiO_2-L-CpRu：一种磁可分离多相脱烯丙基化催化剂

• 发表时间: 2009
• 作者: Shinji Tanaka;Tomoaki Seki;Prasun Kanti Pradhan;Hiroshi Nakatsuka;Masato Kitamura
• 通讯作者: Masato Kitamura