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Asymmetric Hydrogenation of Ketones and Imines with Poly-Coordinated Chiral Catalysts

多配位手性催化剂对酮和亚胺的不对称氢化

基本信息

批准号：
18350046
负责人：
OHKUMA Takeshi
金额：
$ 10万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

A series of ruthenium complexes with both chiral diphosphine and diamine ligands was designed and applied to asymmetric hydrogenation of ketones. The obtained results are described below1) Chiral 1,4-diamine IPHAN was prepared from mannitol. The TolBINAP/IPHAN-Ru complex effectively catalyzed asymmetric hydrogenation of 1-tetralones and their analogues in a base containing 2-propanol. The reaction was completed with a substrate-to-catalyst molar ratio (S/C) as high as 55,000 to afford the chiral alcohols in up to 99% enantiomeric excess (ee). Substituted 2-cyclohexenones were also converted to the allylic alcohols in high ee.2) The TolBINAP/PICA-Ru catalyst (PICA=α-picolylamine) achieved asymmetric hydrogenation of tert-alkyl ketones. A series of sterically hindered ketones was hydrogenated with an S/C as high as 100,000 at 20 atm H_2 to produce the chiral alcohols in up to 98% ee.3) A library of Ru complexes with chiral diphosphine ligands and chiral diamine ligands was made for systematic screening of chiral catalysts in asymmetric hydrogenation of various ketones. For this purpose, a series of chiral 1,2-diamine ligands was prepared from amino acids. Among of them a chiral N,N-dimethyl-1,2-diamine, DMAPEN, showed unique features. The TolBINAP/DMAPEN-Ru catalyzed hydrogenation of arylglyoxal dialkylacetals afforded the α-hydroxy acetals in up to 98% ee.4) Aromatic imines were hydrogenated with chiral Ru complexes under basic conditions.5) LiCl, one of the simplest lithium salts, efficiently catalyzed a reaction of aldehydes and (CH_3)_3SiCN under solvent free conditions. The cyanosilylation of a series of aromatic, aliphatic, and vinylic aldehydes completed with an S/C as high as 100,000 at ambient temperature.Topics 1) to 3) have expanded into collaboration projects with chemical industries.The investigator (Takeshi Ohkuma) received JSPS Prize from Japan Society for the Promotion of Science in 2007.

设计了一系列同时含有手性双膦和手性二胺配体的钌配合物，并将其用于酮的不对称氢化反应。所得结果描述如下：1）由甘露醇制备手性1，4-二胺IPHAN。TolBINAP/IPHAN-Ru配合物能有效催化1-四氢萘酮及其类似物在含2-丙醇的碱中的不对称氢化。在底物与催化剂的摩尔比（S/C）高达55，000的情况下完成反应，得到高达99%对映体过量（ee）的手性醇。2）TolBINAP/PICA-Ru催化剂（PICA=α-吡啶甲基胺）实现了叔烷基酮的不对称加氢。在20 atm H_2下，一系列具有空间位阻的酮被氢化，其S/C高达100，000，生成了高达98%ee的手性醇。3）建立了手性双膦配体和手性二胺配体的Ru配合物库，用于各种酮的不对称氢化的手性催化剂的系统筛选。为此目的，以氨基酸为原料合成了一系列手性1，2-二胺配体。其中手性N，N-二甲基-1，2-二胺DMAPEN具有独特的性质。4）在碱性条件下，手性钌配合物催化芳香亚胺的加氢反应; 5）在无溶剂条件下，LiCl（一种最简单的锂盐）催化醛与（CH_3）_3SiCN的反应。在常温下，以高达100，000的S/C完成了芳香族、脂肪族和乙烯基醛的氰基硅烷化反应。课题1）~ 3）已扩展到与化学产业界的合作项目。研究者（大沼武）于2007年获得日本科学振兴会JSPS奖。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Asymmetric hydrogenation of aromatic, aliphatic, and α,β-unsaturated acyl silanes catalyzed by tol-binap/pica ruthenium(II) complexes:: Practical synthesis of optically active α-hydroxysilanes

DOI：
10.1002/anie.200704696
发表时间：
2008-01-01
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
影响因子：
16.6
作者：
Arai, Noriyoshi;Suzuki, Ken;Ohkuma, Takeshi
通讯作者：
Ohkuma, Takeshi

On the synthesis of protopine alkaloids

DOI：
10.1021/jo071038y
发表时间：
2007-09-14
期刊：
JOURNAL OF ORGANIC CHEMISTRY
影响因子：
3.6
作者：
Wada, Yasuhiro;Kaga, Harumi;Orito, Kazuhiko
通讯作者：
Orito, Kazuhiko

ルテニウム錯体を用いるアルデヒド類の不斉シアノシリル化

使用钌络合物对醛进行不对称氰基甲硅烷基化

DOI：
发表时间：
2008
期刊：
影响因子：
0
作者：
Yoshimichi Morimoto;Yasutaka Fujioka;Hideki Amii;A.Iida;K. Aoki;Yoshimichi Morimoto;大熊毅
通讯作者：
大熊毅

Tailor-made触媒を用いるケトン類の不斉水素化

使用定制催化剂进行酮的不对称氢化

DOI：
发表时间：
2008
期刊：
Organometallic News
影响因子：
0
作者：
Teruyuki Kondo;Takashi Fukuda;Kenji Wada;Take-aki Mitsudo;T. Ozawa;N. Arai;小澤岳昌;Teruyuki Kondo;K. Aoki;近藤輝幸;大熊毅
通讯作者：
大熊毅

Synthesis of a 3-Arylisoquinoline Alkajoid, Decumbene B.

3-芳基异喹啉生物碱、Decumbene B 的合成。