Nitrile Oxide 1,3-Dipolar Cycloaddition by Dehydration of Nitromethane Derivatives Under Continuous Flow Conditions
Malte Brasholz A , Simon Saubern A and G. Paul Savage A B
+ Author Affiliations
- Author Affiliations
A CSIRO Materials Science and Engineering, Private Bag 10, Clayton South MDC, Vic. 3169, Australia.
B Corresponding author. Email: paul.savage@csiro.au
Australian Journal of Chemistry 64(10) 1397-1401 https://doi.org/10.1071/CH11079
Submitted: 16 February 2011 Accepted: 3 June 2011 Published: 23 August 2011
Abstract
Aliphatic nitrile oxides were generated in situ, by dehydration of terminal nitro compounds, and reacted with dipolarophiles using continuous flow techniques to afford substituted isoxazolines. The yields of cycloadducts were comparable with traditional flask-based reactions but reaction times were much shorter. In-line scavenger cartridges conveniently removed by-products and unreacted reagents to give almost pure crude products. The process was demonstrated up to gram scale.
References
[1] R. Huisgen, Angew. Chem. Int. Ed. Engl. 1963, 2, 565.| Crossref | GoogleScholarGoogle Scholar |
[2] A. Hassner, in Synthesis of Heterocycles via Cycloadditions 2008 (Ed. R. R. Gupta) (Springer: Berlin).
[3] C. Spiteri, P. Sharma, F. Zhang, S. J. F. Macdonald, S. Keeling, J. E. Moses, Chem. Commun. 2010, 46, 1272.
| Crossref | GoogleScholarGoogle Scholar |
[4] C. Spiteri, C. Mason, F. Zhang, D. J. Ritson, P. Sharma, S. Keeling, J. E. Moses, Org. Biomol. Chem. 2010, 8, 2537.
| Crossref | GoogleScholarGoogle Scholar |
[5] P. Caramella, P. Grünanger, in 1,3-Dipolar Cycloaddition Chemistry 1984, Vol. 1, pp. 291–392 (Ed A. Padwa) (John Wiley & Sons: New York, NY).
[6] C. J. Easton, C. M. M. Hughes, G. P. Savage, G. W. Simpson, in Cycloaddition Reactions of Nitrile Oxides with Alkenes 1994, Vol. 60, pp. 261–327 (Ed. A. R. Katritzky) (Academic Press: San Diego, CA).
[7] P. Grunanger, P. Vita-Finzi, Isoxazoles – Part 1. Chemistry of Heterocyclic Compounds 1991 (Eds A. Weissberger, E. C. Taylor) (Wiley: New York, NY).
[8] B. M. Kelly-Basetti, I. Krodkiewska, W. H. F. Sasse, G. P. Savage, G. W. Simpson, Tetrahedron Lett. 1995, 36, 327.
| Crossref | GoogleScholarGoogle Scholar |
[9] A. Singh, G. P. Roth, Org. Lett. 2011, 13, 2118.
| Crossref | GoogleScholarGoogle Scholar |
[10] C. K. Y. Lee, C. J. Easton, G. P. Savage, G. W. Simpson, Arkivoc 2006, 3, 175.
[11] B. M. Kelly-Basetti, M. F. Mackay, S. M. Pereira, G. P. Savage, G. W. Simpson, Heterocycles 1994, 37, 529.
| Crossref | GoogleScholarGoogle Scholar |
[12] S. Dadiboyena, J. Xu, A. T. Hamme, Tetrahedron Lett. 2007, 48, 1295.
| Crossref | GoogleScholarGoogle Scholar |
[13] S. M. Pereira, G. P. Savage, G. W. Simpson, R. J. Greenwood, M. F. Mackay, Aust. J. Chem. 1993, 46, 1401.
| Crossref | GoogleScholarGoogle Scholar |
[14] J. Xu, A. Hamme, Synlett 2008, 919.
[15] R. Newton, G. P. Savage, Aust. J. Chem. 2008, 61, 432.
| Crossref | GoogleScholarGoogle Scholar |
[16] N. J. Beattie, C. L. Francis, A. J. Liepa, G. P. Savage, Aust. J. Chem. 2010, 63, 445.
| Crossref | GoogleScholarGoogle Scholar |
[17] G. P. Savage, Curr. Org. Chem. 2010, 14, 1478.
| Crossref | GoogleScholarGoogle Scholar |
[18] H. Feuer, K. Torssell, in Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis: Novel Strategies in Synthesis 2008 (John Wiley and Sons: New Jersey).
[19] G. P. Savage, G. T. Wernert, Aust. J. Chem. 2005, 58, 877.
| Crossref | GoogleScholarGoogle Scholar |
[20] S. J. Barrow, C. J. Easton, G. P. Savage, G. W. Simpson, Tetrahedron Lett. 1997, 38, 2175.
| Crossref | GoogleScholarGoogle Scholar |
[21] T. Mukaiyama, T. Hoshino, J. Am. Chem. Soc. 1960, 82, 5339.
| Crossref | GoogleScholarGoogle Scholar |
[22] X. Y. Mak, P. Laurino, P. H. Seeberger, Beilstein J. Org. Chem. 2009, 5,
| Crossref | GoogleScholarGoogle Scholar |
[23] C. Wiles, P. Watts, Eur. J. Org. Chem. 2008, 2008, 1655.
| Crossref | GoogleScholarGoogle Scholar |
[24] S. V. Ley, I. R. Baxendale, Chima 2008, 62, 162.
| Crossref | GoogleScholarGoogle Scholar |
[25] A. Kirschning, W. Solodenko, K. Mennecke, Chem. – Eur. J. 2006, 12, 5972.
| Crossref | GoogleScholarGoogle Scholar |
[26] I. R. Baxendale, J. Deeley, C. M. Griffiths-Jones, S. V. Ley, S. Saaby, G. K. Tranmer, Chem. Commun. 2006, 2566.
| Crossref | GoogleScholarGoogle Scholar |
[27] K. Jähnisch, V. Hessel, H. Löwe, M. Baerns, Angew. Chem. Int. Ed. 2004, 43, 406.
| Crossref | GoogleScholarGoogle Scholar |
[28] A. Palmieri, S. V. Ley, A. Polyzos, M. Ladlow, I. R. Baxendale, Beilstein J. Org. Chem. 2009, 5, 23.
| Crossref | GoogleScholarGoogle Scholar |
[29] A. Polyzos, M. O’Brien, T. P. Petersen, I. R. Baxendale, S. V. Ley, Angew. Chem. Int. Ed. 2011, 50, 1190.
| Crossref | GoogleScholarGoogle Scholar |
[30] S. Castellano, L. Tamborini, M. Viviano, A. Pinto, G. Sbardella, P. Conti, J. Org. Chem. 2010, 75, 7439.
| Crossref | GoogleScholarGoogle Scholar |
[31] M. Brasholz, J. M. Macdonald, S. Saubern, J. H. Ryan, A. B. Holmes, Chem. – Eur. J. 2010, 16, 11471.
| Crossref | GoogleScholarGoogle Scholar |
[32] M. Brasholz, B. A. Johnson, J. M. Macdonald, A. Polyzos, J. Tsanaktsidis, S. Saubern, A. B. Holmes, J. H. Ryan, Tetrahedron 2010, 66, 6445.
| Crossref | GoogleScholarGoogle Scholar |
[33] A. Palmieri, S. V. Ley, K. Hammond, A. Polyzos, I. R. Baxendale, Tetrahedron Lett. 2009, 50, 3287.
| Crossref | GoogleScholarGoogle Scholar |
[34] C. H. Hornung, C. Guerrero-Sanchez, M. Brasholz, S. Saubern, J. Chiefari, G. Moad, E. Rizzardo, S. H. Thang, Org. Process Res. Dev. 2011, 15, 593.
| Crossref | GoogleScholarGoogle Scholar |
[35] Y. Basel, A. Hassner, Synthesis 1997, 1997, 309.
| Crossref | GoogleScholarGoogle Scholar |
[36] L. Cecchi, F. De Sarlo, F. Machetti, Eur. J. Org. Chem. 2006, 2006, 4852.
| Crossref | GoogleScholarGoogle Scholar |
[37] D. Webb, T. F. Jamison, Chem. Sci. 2010, 1, 675.
| Crossref | GoogleScholarGoogle Scholar |
[38] G. K. Tranmer, W. Tam, Org. Lett. 2002, 4, 4101.
| Crossref | GoogleScholarGoogle Scholar |
[39] L. Cecchi, F. De Sarlo, F. Machetti, Chem. – Eur. J. 2008, 14, 7903.
| Crossref | GoogleScholarGoogle Scholar |
[40] O. Moriya, H. Takenaka, M. Iyoda, Y. Urata, T. Endo, J. Chem. Soc. Perkin Trans. 1 1994, 413.
| Crossref | GoogleScholarGoogle Scholar |
