新型手性路易斯碱的合成及其在手性脂肪胺制备中的应用

Synthesis of a Novel Chiral Lewis Base and Its Application in Preparation of Chiral Aliphatic Amines

以氯霉胺为原料,经两步缩合反应合成了一个新型手性路易斯碱——N-[(4S,5S)-4-(4-硝基苯基)-2-十一烷基-1,3-二噁烷烃-5-基]吡啶甲酰胺(3);以三氯硅烷为氢源,3为催化剂,2-十三烷酮与芳香胺原位生成的脂肪亚胺经氢化硅烷化反应合成了两个手性脂肪胺,收率高达95%,对映选择性最高为16%,其结构经1H NMR和13C NMR确证。结果表明:在该反应中,3具有较佳的催化活性,但立体选择性不佳。

A novel Lewis base catalyst bearing long alkyl chain group, N-[ （4S,5S）-4-（4-nitrophe- nyl）-2-undecyl-1,3-dioxan-5-yl] picolinamide（3）, was synthesized by a two-step condensation reac- tion using （ 1S ,2S） -2-amino-l-（4-nitrophenyl） propane-1,3-diol as the starting material. Two chiral aliphatic amines were obtained by hydrosilylation of aliphatic imines generated in situ catalyzed by 3 under mild condition using trichlorosilane as the reducing agent. The yield was up to 95% and enantioselectivity was only 16%. The structures were confirmed by 1H NMR and 13C NMR. The results showed that 3 exhibit high catalytic activity, but low stereoselectivitv.