Design of novel functional oxide and its application to catalytic reactions

新型功能氧化物的设计及其在催化反应中的应用

基本信息

批准号：
16590001
负责人：
NAKAJIMA Makoto
金额：
$ 2.18万
依托单位：
Kumamoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

Organocatalysis has been one of the current hot topics in the field of synthetic chemistry because of its environmentally benign nature. Recently, asymmetric organocatalyses utilizing neutral Lewis bases attracted much attention because it led to the emergence of new types of chiral ligands based on functional oxide compounds. Phosphine oxide has high polarity and relatively low Bronsted basicity, whose reactivity is expected to be similar to those of such Lewis bases. Moreover, various types of chiral phosphine oxides can be easily obtained by the simple oxidation of commercially available chiral phosphines. However, the examples of the application of chiral phosphine oxides to asymmetric organocatalyses are still limited. We investigated the catalytic activity of BINAPO, which is easily prepared from the most common chiral phosphine ligand BINAP. We found that BINAPO was an effective catalyst for the enantioselective allylation of aldehyde with allyltrichlorosilane and the enantiosel … More ective aldol reaction of trichlorosilyl enol, wherein the allylated adducts or aldol adducts were obtained in high diastereo- and enantioselectivities (up tp 96% ee). BINAPO was found to be effective in the enantioselective ring opening of meso-epoxides with tetrachlorosilane in the presence of diisopropylethylamine, affording the corresponding chlorohydrins in high enantioselectivities of up to 90% ee. An aldol reaction of trimethoxysilyl enol ether catalyzed by lithium binaphthoxide was also developed. The aldol reaction of trimethoxysilyl enol ether derived from cyclohexanone under anhydrous conditions predominantly afforded the anti-aldol adduct with moderate enantioselectivity, whereas the reaction under hydrous conditions predominantly resulted in the syn-adduct and the enantioselectivity of the syn-adduct was considerably improved. The best enantioselectivity was obtained in the reaction of trimethoxysilyl enol ether derived from 1-indanone with cyclohexanecarboxaldehyde (97% ee (syn)). This is the first example of an aldol reaction of trimethoxysilyl enol ether catalyzed by a chiral base. Less

有机催化因其对环境友好的性质而成为当前合成化学领域的热门话题之一，最近，利用中性路易斯碱的不对称有机催化引起了人们的广泛关注，因为它导致了基于功能性氧化物化合物的新型手性配体的出现。氧化膦具有高极性和相对较低的布朗斯台德碱度，其反应活性预计与此类路易斯碱相似，而且各种类型的手性氧化膦都可以。通过简单氧化市售手性膦即可轻松获得。然而，我们研究了 BINAPO 的催化活性，该手性氧化膦可以很容易地由最常见的手性膦配体制备。我们发现 BINAPO 是醛与烯丙基三氯硅烷对映选择性烯丙基化的有效催化剂。和三氯甲硅烷基烯醇的对映醇醛反应，以高非对映选择性和对映选择性（高达 96% ee）获得强烯丙基化加合物或羟醛加合物，发现 BINAPO 可有效地对内消旋环氧化物进行对映选择性开环。在二异丙基乙胺存在下与四氯硅烷反应，以高浓度得到相应的氯醇还开发了联萘锂催化的三甲氧基硅烷基烯醇醚的羟醛反应，该反应主要在无水条件下由环己酮衍生的三甲氧基硅烷基烯醇醚的羟醛反应提供了具有中等对映选择性的反羟醛加合物。在含水条件下主要产生顺式加合物和对映选择性1-茚满酮衍生的三甲氧基硅基烯醇醚与环己烷甲醛（97% ee (syn)）的反应获得了最佳的对映选择性，这是三甲氧基硅基烯醇醚催化的醇醛缩合反应的第一个例子。更少的手性碱基。

项目成果

期刊论文数量（29）

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 ring opening of meso-epoxides catalyzed by the chiral phosphine oxide BINAPO

DOI：
10.1016/j.tetasy.2005.06.021
发表时间：
2005-07-18
期刊：
TETRAHEDRON-ASYMMETRY
影响因子：
0
作者：
Tokuoka, E;Kotani, S;Nakajima, M
通讯作者：
Nakajima, M

Enantioselective aldol reactions of trichlorosilyl enol ethers catalyzed by the chiral phosphine oxide BINAPO

DOI：
10.1055/s-2006-939725
发表时间：
2006-05-03
期刊：
SYNLETT
影响因子：
2
作者：
Kotani, Shunsuke;Hashimoto, Shunichi;Nakajima, Makoto
通讯作者：
Nakajima, Makoto

The Enantioselective Aldol Reaction of Trimethoxysilyl Enol Ether Catalyzed by Lithium Binaphtholate.

联萘酸锂催化三甲氧基硅烯醇醚的对映选择性羟醛反应。

DOI：
发表时间：
2004
期刊：
Organic Letters 6
影响因子：
0
作者：
Nakajima;M.;Orito;Y.;Ishizuka;T.;Hashimoto;S.
通讯作者：
S.

A new dirhodium(II) carboxamidate complex as a chiral lewis acid catalyst for enantioselective hetero-Diels-Alder reactions

DOI：
10.1002/anie.200453821
发表时间：
2004-01-01
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
影响因子：
16.6
作者：
Anada, M;Washio, T;Hashimoto, S
通讯作者：
Hashimoto, S

The Enantioselective Aldol Reaction of Trimethoxysilyl Enol Ether Catalyzed by Lithium Binaphtholate

联萘酸锂催化三甲氧基硅烯醇醚的对映选择性羟醛反应

DOI：
发表时间：
2004
期刊：
Organic Letters 6
影响因子：
0
作者：
Nakajima;M.;Kotani;S.;Ishizuka;T.;Hashimoto;S.;Manabu Yamakuchi;Ryo Tokuda;Makoto Nakajima;Makoto Nakajima
通讯作者：
Makoto Nakajima