功能化分子筛催化氮杂环丙烷与异硫氰酸酯[3+2]环加成反应的研究
|
摘要
主要研究了固体酸催化剂对氮杂环丙烷与异硫氰酸酯间的[3+2]环加成反应的催化效果,并对反应展开了一系列底物拓展。实验结果表明,在该催化体系下,反应都有不错的收率。并且通过催化剂重复性实验,也可以发现,经过多次重复利用的固体酸也可以起到有效的催化作用。
In this research,an efficient, simple, and general route for the[3+2] cycloaddition reaction of aziridines with isothiocyanates been described using functionlized zeolite catalysis inair.Using SBA-15-PW as catalyst, a series of heterocycles were obtained from aziridines in good to high yields.Moreover,reusability study showed that the catalyst SBA-15-PW could be reused at least for 5 runs without losing significant catalytic activity after a simple washing.
In this research,an efficient, simple, and general route for the[3+2] cycloaddition reaction of aziridines with isothiocyanates been described using functionlized zeolite catalysis inair.Using SBA-15-PW as catalyst, a series of heterocycles were obtained from aziridines in good to high yields.Moreover,reusability study showed that the catalyst SBA-15-PW could be reused at least for 5 runs without losing significant catalytic activity after a simple washing.
引文
[1] Liu P. Recent developments inregioselective ring opening of aziridines[J]. Tetrahedron, 2010, 66(14):2549-2560.
[2] Butler C D, Inman A G, Alper H. Room temperature ring-opening cyclization reactions of 2-vinylaziridines with isocyanates, carbodiimides, and isothiocyanates catalyzed by[Pd(OAc)2]/PPh3[J]. J. Org. Chem., 2000, 65(19):5887.
[3] Munegumi T, Azumaya I, Kato T,et al.[3+2] Crosscoupling reactions of aziridines with isocyanates catalyzed by nickel(II)iodide[J]. Org. Lett., 2006, 8(3):379-382.
[4] Pfeil E, Milzner K. Synthesis of 2-oxazoline-2-amines and 2-thiazoline-2-amines by reaction of aziridinium tetrafluoroborate with isocyanates and isothiocyanates[J].Angew. Chem. Int. Ed. Engl., 1966, 5(7):667.
[5] Tascedda P, Du觡ach E. Electrosynthesis of cyclic carbamates from aziridines and carbon dioxide[J]. Chem. Commun., 2000, 449-450.
[6] Nadir U K, Basu N. Unsual cycloaddition reactions of ubstituted N-(arylsulfonyl)aziridines with aryl and alkyl isothiocyanates in the presence of sodium-iodide as catayst[J]. J. Org. Chem.,1995, 60(5):1458-1460.
[7] Nomura R, Nakano T, Nishio Y,et al. Regioselective cycloaddition of 1,2-disubstituted aziridines to heterocumulenes catalyzed by organoantimony halides[J]. Chem.Ber., 1989, 122(12):2407-2409.
[2] Butler C D, Inman A G, Alper H. Room temperature ring-opening cyclization reactions of 2-vinylaziridines with isocyanates, carbodiimides, and isothiocyanates catalyzed by[Pd(OAc)2]/PPh3[J]. J. Org. Chem., 2000, 65(19):5887.
[3] Munegumi T, Azumaya I, Kato T,et al.[3+2] Crosscoupling reactions of aziridines with isocyanates catalyzed by nickel(II)iodide[J]. Org. Lett., 2006, 8(3):379-382.
[4] Pfeil E, Milzner K. Synthesis of 2-oxazoline-2-amines and 2-thiazoline-2-amines by reaction of aziridinium tetrafluoroborate with isocyanates and isothiocyanates[J].Angew. Chem. Int. Ed. Engl., 1966, 5(7):667.
[5] Tascedda P, Du觡ach E. Electrosynthesis of cyclic carbamates from aziridines and carbon dioxide[J]. Chem. Commun., 2000, 449-450.
[6] Nadir U K, Basu N. Unsual cycloaddition reactions of ubstituted N-(arylsulfonyl)aziridines with aryl and alkyl isothiocyanates in the presence of sodium-iodide as catayst[J]. J. Org. Chem.,1995, 60(5):1458-1460.
[7] Nomura R, Nakano T, Nishio Y,et al. Regioselective cycloaddition of 1,2-disubstituted aziridines to heterocumulenes catalyzed by organoantimony halides[J]. Chem.Ber., 1989, 122(12):2407-2409.