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.

一系列具有手性双氨和二氨基配体的唯一复合物设计并应用于酮的不对称氢化。在下面描述了获得的结果1）手性1,4-二胺iphan是从甘露醇制备的。 TOLBINAP/IPHAN-RU复合物有效地催化了含有2-丙醇的碱中1-二脑酮及其类似物的不对称氢化。用取代的2-环己烯酮在高EE中转换为垂体醇。2）TOLBINAP/PICA-RU催化剂（PICA =α-五甲基胺）实现了tert-Alkyl酮的不对称氢化。 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.为此，用氨基酸制备了一系列手性1,2-二胺配体。其中包括手性N，N-二甲基-1,2-二胺Dmapen，显示出独特的特征。 TOLBINAP/DMAPEN-RU催化芳基氧化二烷基乙酸酯的氢化为α-羟基乙酸提供了多达98％EE.4）芳族在基本条件下用手性RU络合物氢化了芳族芳族。5）licl。（CH_3）_3SICN在无溶液的条件下。一系列芳香，脂肪族和vinylic醛在环境温度下完成的S/C高达100,000的氰基化。TOPOPICS1）至3）已扩展到与化学工业的合作项目。

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）

Synthesis of a 3-Arylisoquinoline Alkajoid, Decumbene B.

3-芳基异喹啉生物碱、Decumbene B 的合成。

DOI：
发表时间：
2007
期刊：
Eur. J. Org. Chem.
影响因子：
0
作者：
J.Chen;K.Aoki;T.Nishiumi;T.Li;Kenta Takai;Y. Wada
通讯作者：
Y. Wada

Solution Structure and Behavior of trans-RuH (η^1・BH_4)(binap)(1,2-diamine) Complexes.

反式RuH (η^1・BH_4)(binap)(1,2-二胺)配合物的溶液结构和行为。

DOI：
发表时间：
2006
期刊：
Magn. Reson. Chem. 44
影响因子：
0
作者：
A. Iida;I. Osada;R. Nagase;T. Misaki;Y. Tanabe;T.Ohkuma;青木幸一;Hideki Amii;N.Arai;R. Nagase;K.Aoki;C. A. Sandoval
通讯作者：
C. A. Sandoval

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

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