Attempted Synthesis and Unexpected β-Fragmentation of a Hindered β-Keto Nitroxide
Chris Edwards A , Peter C. Healy A , W. Ken Busfield A , Ezio Rizzardo B , San H. Thang B and Ian D. Jenkins C DA School of Natural Sciences, Griffith University, Brisbane, Qld 4111, Australia.
B CSIRO Materials Science and Engineering, Bayview Avenue, Clayton, Vic. 3168, Australia.
C Griffith Institute for Drug Discovery, Griffith University, Brisbane, Qld 4111, Australia.
D Corresponding author. Email: i.jenkins@griffith.edu.au
Australian Journal of Chemistry 70(10) 1106-1109 https://doi.org/10.1071/CH17203
Submitted: 11 April 2017 Accepted: 11 May 2017 Published: 31 May 2017
Abstract
The attempted synthesis of a β-keto imidazolidinone nitroxide by oxidation of the β-hydroxy imidazolidinone precursor with hydrogen peroxide and sodium tungstate led to an unexpected ring-opening reaction to produce 1,4-diazaspiro[4.5]dec-1-en-3-oxo-2-pentanoic acid 1-oxide (13) in high yield. The structure of 13 was confirmed by X-ray crystallographic analysis. A β-fragmentation mechanism is suggested for the oxidative ring-opening reaction.
References
[1] (a) D. H. Solomon, E. Rizzardo, P. Cacioli, U.S. Patent 4,581,429 1986.(b) E. Rizzardo, Chem. Aust 1987, 54, 32.
(c) G. Moad, E. Rizzardo, D. H. Solomon, in Comprehensive Polymer Science (Eds G. C. Eastmond, A. Ledwith, S. Russo, P. Sigwalt) 1989, Vol. 3, p. 141 (Pergamon: London).
(d) E. Rizzardo, D. H. Solomon, Aust. J. Chem. 2012, 65, 945.
| Crossref | GoogleScholarGoogle Scholar |
[2] Y. K. Chong, F. Ercole, G. Moad, E. Rizzardo, S. H. Thang, A. G. Anderson, Macromolecules 1999, 32, 6895.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXmt12ltLo%3D&md5=335fc0dc7c7443856960de2d2f698adcCAS |
[3] R. Braslau, H. Kuhn, L. C. Burrill, K. Lanham, C. J. Stenland, Tetrahedron Lett. 1996, 37, 7933.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28Xms1ymsb8%3D&md5=7975efe4fd1487e461611ac32272b273CAS |
[4] T. Toda, S. Morimura, E. Mori, S. Horiuchi, K. Murayama, Bull. Chem. Soc. Jpn. 1971, 44, 3445.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE38XlvFGhtg%3D%3D&md5=def611405ea3a8f11529fe97e441d496CAS |
[5] A. G. Anderson, A. Gridnev, G. Moad, E. Rizzardo, S. H. Thang, PCT Int. Appl., WO 9830601 A2 19980716 1998.
[6] J. A. Cella, J. A. Kelley, E. F. Kenehan, J. Org. Chem. 1975, 40, 1860.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2MXksVartb8%3D&md5=51ab010531a1eadde0620440f6fe5086CAS |
[7] B. Ganem, J. Org. Chem. 1975, 40, 1988.
[8] J. Einhorn, C. Einhorn, F. Ratajczak, J.-L. Pierre, J. Org. Chem. 1996, 61, 7452.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28XmtF2htrs%3D&md5=d58a2f1b620d080f02b7d4234b458670CAS |
[9] Z. Ma, J. M. Bobbitt, J. Org. Chem. 1991, 56, 6110.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXmtlWgtrk%3D&md5=ab2a62be187213aae5809033c2a76aaaCAS |
[10] C. Michel, P. Belanzoni, P. Gamez, J. Reedijk, E. Baerends, Inorg. Chem 2009, 48, 11909.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhsVyjt7bL&md5=4366b24886ca8b53f6ee74da51f1c9efCAS |
[11] C. Bischoff, E. Schroder, J. Prakt. Chem. 1988, 330, 379.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1MXnsVyjuw%3D%3D&md5=14d46f0c87d71319d71000db55243e1dCAS |
[12] Molecular Structure Corporation, MSC/AFC7 Diffractometer Control for Windows Version 1.02 1999 (MSC: The Woodlands, TX).
[13] A. Altomare, G. L. Cascarano, C. Giacovazzo, A. Guagliardi, J. Appl. Cryst. 1994, 27, 435.
[14] Molecular Structure Corporation, TeXsan for Windows. Single-Crystal Structure Analysis Software Version 1.06 2001 (MSC: The Woodlands, TX).
[15] L. J. Farrugia, J. Appl. Cryst. 2012, 45, 849.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhtVKltbzK&md5=4b3d869e655994706c63c7c42cc72f36CAS |
[16] G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64, 112.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhsVGhurzO&md5=933d4ded754510f3d6dd59e45c48aab3CAS |
[17] A. L. Spek, J. Appl. Cryst. 2003, 36, 7.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXltlChtw%3D%3D&md5=a70469aed31b7683d455883cff6e2596CAS |
