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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.

为了开发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氰对各种n取代亚胺的对端选择性加成。首先，我们研究了手性席夫碱-钛醇氧配合物对醛类化合物的三甲基硅基氰化反应的催化作用。我们发现使用手性钛配合物可以获得较高的化学产率，但光产率仅为20%。手性钛配合物含手性二萘酚衍生物，光产率也很低。然后研究了阳离子手性BINAP-钯配合物催化的反应。采用原位制备和分离的配合物，虽然化学产率很高，但光学产率都很低。基于以上结果，我们改变了合成光活性胺的策略，即钯配合物催化不对称烯丙基胺化。我们成功地合成了具有P， n双齿配体的新型钯催化剂。这些新型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收率在80%以上。目前，不对称胺化反应正在研究中。