手性硼酸酯介入的不对称合成3:(R)-或(S)-1,1'-联-2-萘酚硼酸-(S)-脯氨酸酐促进的前手性亚胺的不对称硼烷还原  

Chiral Borate Esters in Asymmetric Synthesis 3. Asymmetric Borane Reduction of Prochiral Imines Promoted by (R)- or (S)-1,1′-Bi-2-naphthoxyboric Acid (S)-Proline Anhydride

作　　者：单自兴[1] 王铨[1] 

机构地区：[1]武汉大学化学系,武汉430072

出　　处：《有机化学》2005年第6期720-723,共4页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.29972033;20372053)资助项目.

摘　　要：手性螺硼酸酯(R)-或(S)-1,1'-联-2-萘酚硼酸-(S)-脯氨酸酐[(R,S)-1或(S,S)-1]对前手性亚胺硼烷还原的不对称催化活性被观察到.在(R,S)-1或(S,S)-1存在下,由前手性二烷基酮或烷基苯酮与苯胺缩合生成的前手性亚胺在THF中被硼烷还原,高产率地给出手性仲胺,其对映体纯度高达74%ee.其中,三种手性仲胺[N-(2-戊基)苯胺,N-(3-甲基-2-丁基)苯胺和N-(4-甲基-2-戊基)苯胺]系首次合成.Asymmetric catalytic activity of chiral spiroborate esters, (R)- or (S)-1,1'-bi-2-naphthoxyboric acid (S)-proline anhydride [(R,S)-1 or (S,S)-1], toward borane reduction of prochiral imines has been observed. In the presence of (R,S)-1 or (S,S)-1, prochiral imines generated from condensation of aniline and a prochiral dialkyl ketone or alkylphenyl ketone were reduced by borane in THF to give chiral secondary amines in high yield and up to 74% ee. Among them, N-(2-pentyl)aniline, N-(3-methyl-2-butyl)aniline and N-(4-methyl-2-pentyl)aniline have not been reported before.

关 键 词：手性亚胺 2-萘酚 硼酸酯 不对称合成 还原 硼烷 酸酐 氨 对映体纯度 催化活性 二烷基酮 苯胺 THF 烷基苯 高产率 仲胺 戊基 甲基 

分 类 号：O627.4[理学—有机化学]