Organic Letters
Letter
(7) Dammacco, M.; Degennaro, L.; Florio, S.; Luisi, R.; Musio, B.;
Altomare, A. J. Org. Chem. 2009, 74, 6319.
aziridines 3w and 3x to p-tolualdehyde was considerably
accelerated (Table 3, entries 8−9). On the other hand, when
ethylenediamine was employed to undergo the ring expansion,
a complex mixture was obtained (Table 3, entry 10). The
produced crude aziridines were subjected to the next
isomerization step without further purification, by which the
corresponding β-nitroenamines 8q−x were furnished in
satisfactory yields (Table 1). Regardless of different N-
substituents in 3, β-nitroenamines 8 were formed with high
Z-selectivity.
In conclusion, we have developed an efficient and highly
diastereoselective one-pot synthesis of trans-N-alkyl-C-nitro-
aziridines 3 upon treatment of nitroalkenes 1 with aliphatic
amines 2 and NCS under mild conditions. The resultant
aziridines 3 were isomerized into functionalized (Z)-β-nitroen-
amines 8 with high diastereoselectivity through Lewis acid
mediated ring opening and rearrangement. Further efforts in
the application of these protocols for synthesizing versatile
functionalized compounds is under investigation in our group.
(8) Ciogli, A.; Fioravanti, S.; Gasparrini, F.; Pellacani, L.; Rizzato, E.;
Spinelli, D.; Tardella, P. A. J. Org. Chem. 2009, 74, 9314.
(9) (a) Schweitzer-Chaput, B.; Keita, M.; Milcent, T.; Ongeri, S.;
Crousse, B. Tetrahedron 2012, 68, 7028. (b) Zibinsky, M.; Butkevich,
A. N.; Kuznetsov, M. A. Tetrahedron Lett. 2008, 49, 5505. (c) Person,
H.; Tonnard, F.; Foucaud, A.; Fayat, C. Tetrahedron Lett. 1973, 14,
2495.
(10) (a) Fioravanti, S.; Pellacani, L.; Vergari, M. C. J. Org. Chem.
2013, 78, 8203. (b) Fioravanti, S.; Marchetti, F.; Pellacani, L.; Ranieri,
L.; Tardella, P. A. Tetrahedron: Asymmetry 2008, 19, 231.
(c) Fioravanti, S.; Pellacani, L.; Stabile, S.; Tardella, P. A. Tetrahedron
1998, 54, 6169. (d) Fioravanti, S.; Pellacani, L.; Stabile, S.; Tardella, P.
A. Tetrahedron Lett. 1997, 38, 3309.
(11) (a) Stukan, E. V.; Makarenko, S. V.; Trukhin, E. V.;
Berestovitskaya, V. M. Russ. J. Gen. Chem. 2010, 80, 2460.
(b) Berestovitskaya, V. M.; Makarenko, S. V.; Bushmarinov, I. S.;
Lyssenko, K. A.; Smirnov, A. S.; Stukan’, A. E. V. Russ. Chem. Bull.
2009, 58, 1023.
(12) (a) Tronchet, J. M. J.; Pallie, K. D.; Rey, F. B. J. Carbohydr.
Chem. 1985, 4, 29. (b) Edasery, J. P.; Cromwell, N. H. J. Heterocycl.
Chem. 1979, 16, 831.
(13) Hao, F.; Asahara, H.; Nishiwaki, N. Tetrahedron 2017, 73, 1255.
(14) (a) Fedotova, A. I.; Komarova, T. A.; Romanov, A. R.; Ushakov,
I. A.; Legros, J.; Maddaluno, J.; Rulev, A. Y. Tetrahedron 2017, 73,
1120. (b) Azzena, U.; Dettori, G.; Pisano, L.; Musio, B.; Luisi, R. J.
Org. Chem. 2011, 76, 2291. (c) Affortunato, F.; Florio, S.; Luisi, R.;
Musio, B. J. Org. Chem. 2008, 73, 9214. (d) Midura, W. H. Tetrahedron
Lett. 2007, 48, 3907. (e) Cardillo, G.; Casolari, S.; Gentilucci, L.;
Tomasini, C. Angew. Chem., Int. Ed. Engl. 1996, 35, 1848.
(15) (a) Barbero, M.; Cadamuro, S.; Dughera, S. Synth. Commun.
2013, 43, 758. (b) Ziyaei-Halimehjani, A. Z.; Saidi, M. R. Tetrahedron
Lett. 2008, 49, 1244.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Detailed optimization, experimental procedures, charac-
1
terization data including copies of H and 13C NMR
Crystallographic data (CIF)
(16) (a) Han, L.; Feng, Y.; Luo, M.; Yuan, Z.; Shao, X.; Xu, X.; Li, Z.
Tetrahedron Lett. 2016, 57, 2727. (b) Zeng, H.; Yuan, P.; Wang, F.; Xu,
X.; Shao, X.; Li, Z. Tetrahedron Lett. 2016, 57, 4031. (c) Asahara, H.;
Hamada, M.; Nakaike, Y.; Nishiwaki, N. RSC Adv. 2015, 5, 90778.
AUTHOR INFORMATION
Corresponding Authors
■
ORCID
́
(d) Pilipecz, M. V.; Scheiber, P.; Vincze, Z.; Varga, T. R.; Toth, G.;
Nemes, P. Tetrahedron 2014, 70, 4355. (e) Rao, H. S. P.; Parthiban, A.
Org. Biomol. Chem. 2014, 12, 6223. (f) Nakaike, Y.; Hayashi, D.;
Nishiwaki, N.; Tobe, Y.; Ariga, M. Org. Biomol. Chem. 2009, 7, 325.
(17) Kuz’mina, N. V.; Lipina, E. S.; Kropotova, T. Y.; Berkova, G. A.;
Pavlova, Z. F. Russ. J. Org. Chem. 2003, 39, 8.
Present Address
§Department of Applied Chemistry, Faculty of Engineering,
Osaka University, Yamadaoka 2-1, Suita, Osaka 565-0871,
Japan.
(18) Sugihara, Y.; Iimura, S.; Nakayama, J. Chem. Commun. 2002, 21,
134.
(19) (a) Ghorai, M. K.; Tiwari, D. P.; Jain, N. J. Org. Chem. 2013, 78,
7121. (b) Dauban, P.; Malik, G. Angew. Chem., Int. Ed. 2009, 48, 9026.
(c) Nakagawa, M.; Kawahara, M. Org. Lett. 2000, 2, 953.
(d) Ungureanu, I.; Bologa, C.; Chayer, S.; Mann, A. Tetrahedron
Lett. 1999, 40, 5315.
Notes
The authors declare no competing financial interest.
REFERENCES
■
(1) Review: (a) Degennaro, L.; Trinchera, P.; Luisi, R. Chem. Rev.
2014, 114, 7881. (b) Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247.
́
(2) Reviews: (a) Stankovic, S.; D’hooghe, M.; Catak, S.; Eum, H.;
Waroquier, M.; Van Speybroeck, V.; De Kimpe, N.; Ha, H. J. Chem.
Soc. Rev. 2012, 41, 643. (b) de Ceglie, M.; Musio, B.; Affortunato, F.;
Moliterni, A.; Altomare, A.; Florio, S.; Luisi, R. Chem. - Eur. J. 2011,
17, 286. (c) Singh, G. S.; D’hooghe, M.; De Kimpe, N. D. Chem. Rev.
2007, 107, 2080. (d) Padwa, A.; Murphreeb, S. S. ARKIVOC 2006,
2000 (iii), 6. (e) Coldham, I.; Hufton, R. Chem. Rev. 2005, 105, 2765.
(f) Hu, X. E. Tetrahedron 2004, 60, 2701.
(3) Kim, B. M.; Bae, S. J.; So, S. M.; Yoo, H. T.; Chang, S. K.; Lee, J.
H.; Kang, J. S. Org. Lett. 2001, 3, 2349.
(4) Crawley, S. L.; Funk, R. L. Org. Lett. 2006, 8, 3995.
(5) Liew, S. K.; Kaldas, S. J.; Yudin, A. K. Org. Lett. 2016, 18, 6268.
(6) Fukuta, Y.; Mita, T.; Fukuda, N.; Kanai, M.; Shibasaki, M. J. Am.
Chem. Soc. 2006, 128, 6312.
D
Org. Lett. XXXX, XXX, XXX−XXX