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Catalytic asymmetric synthesis of optically active amines and their derivatives

催化不对称合成光学活性胺及其衍生物

基本信息

批准号：
10640579
负责人：
HAYASHI Masahiko
金额：
$ 2.11万
依托单位：
Yamaguchi University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640579/
关键词：
asymmetric synthesis chiral amine palladium catalyst allylamine bidentate ligand tridentate ligand Schiff base titanium complex 不斉合性チタン触媒パラジウム錯体 π-アリル錯体

项目摘要

For the development of the asymmetric synthesis of optically active amines and their derivatives, we examined the enanioselective addition of trimethylsilyl cyanide to a variety of N-substituted imines. At first, we investigated the reaction catalyzed by chiral Schiff base-titanium alkoxide complexes which was very effective for enantioselective trimethylsilylcyanation of aldehydes. We found that by using chiral titanium complexes, high chemical yield was attained, but only unsatisfied optical yield (20% ee) was obtained. The chiral titanium complex bearing chiral binaphthol derivatives was also found to give only low optical yield. Then we examined the reaction catalyzed by cationic chiral BINAP- palladium complex. By using complex of in-situ preparation and isolated one, low optical yield was obtained in both cases though chemical yield was high. Based on the above results we changed the strategy for the synthesis of optically active amines, that is, catalytic asymmetric allylic amination catalyzed by palladium complexes. We have succeeded in the synthesis of novel palladium catalyst having P, N-bidentate ligands. These new catalyst was found to have high catalytic activity and enantioselectivity in catalytic allylic alkylation. The optical yields of the allylic alkylation products were over 80% ee. At present, the asymmetric amination is being examined.

为了发展光学活性胺及其衍生物的不对称合成，我们研究了三甲基硅腈对各种N-取代亚胺的不对称加成反应。首先，我们研究了手性席夫碱-钛醇盐配合物催化的醛的三甲基硅腈化反应。我们发现，使用手性钛配合物，获得了高的化学产率，但只有不满意的光学产率（20%ee）。手性钛配合物轴承手性联萘衍生物也被发现，只有低的光学产率。然后考察了阳离子手性BINAP-钯配合物催化的反应.采用原位合成的配合物和单独合成的配合物，虽然化学产率较高，但光学产率较低。基于上述结果，我们改变了光学活性胺的合成策略，即钯配合物催化的不对称烯丙基胺化反应。我们成功地合成了具有P，N-双齿配体的新型钯催化剂。这些催化剂在催化烯丙基烷基化反应中具有较高的催化活性和对映选择性。烯丙基烷基化产物的光学产率在80%ee以上。目前，不对称胺化反应正在研究中。