|
1,5-(1,7)-Biradicals and Nitrenes Formed by Ring Opening of Hetarylnitrenes
Curt
Wentrup
A
B
and
David
Kvaskoff
A
A
School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, Australia.
B
Corresponding author. Email: wentrup@uq.edu.au
Australian Journal of Chemistry
66(3)
286-296 http://dx.doi.org/10.1071/CH12502
Submitted: 7 November 2012 Accepted: 18 December 2012 Published:
11
February
2013
|  |
|
|
Abstract
Several aromatic and heteroaromatic nitrenes and carbenes undergo photochemical and sometimes also thermal ring opening. Depending on benz-annelation, the ring-opened species may have the character of either nitrenes (for α-annelation) or 1,5-(1,7-)-biradicals (for β-annelation). Both types have been observed, and they are clearly distinguished by their characteristic electron spin resonance spectra. In addition, ring opening of hetarylnitrenes to nitrile ylides can be observed whenever there is a meta-relationship between a ring nitrogen atom and the nitrene (or carbene) centre. The factors governing the two types of ring opening have been investigated. The nitrenes and carbenes are generated by either low temperature Ar matrix photolysis or flash vacuum thermolysis of azides, tetrazoles, triazoles, or diazo compounds with matrix isolation of the products. 
|
References
[1]
C. Wentrup, Acc. Chem. Res. 2011, 44, 393. | CrossRef | CAS | 
[2]
(a) A. Reisinger, P. V. Bernhardt, C. Wentrup, Org. Biomol. Chem. 2004, 2, 246. | CrossRef | CAS | (b) A. Reisinger, R. Koch, P. V. Bernhardt, C. Wentrup, Org. Biomol. Chem. 2004, 2, 1227. | CrossRef | (c) C. Addicott, C. Wentrup, Aust. J. Chem. 2008, 61, 592. | CrossRef |
[3]
A. McCluskey, C. Wentrup, J. Org. Chem. 2008, 73, 6265. | CrossRef | CAS |
[4]
D. Kvaskoff, P. Bednarek, C. Wentrup, J. Org. Chem. 2010, 75, 1600. | CrossRef | CAS |
[5]
D. Kvaskoff, P. Bednarek, L. George, K. Waich, C. Wentrup, J. Org. Chem. 2006, 71, 4049. | CrossRef | CAS |
[6]
P. Bednarek, C. Wentrup, J. Am. Chem. Soc. 2003, 125, 9083. | CrossRef | CAS |
[7]
D. Bégué, G. G. Qiao, C. Wentrup, J. Am. Chem. Soc. 2012, 134, 5339. | CrossRef |
[8]
D. Kvaskoff, M. Vosswinkel, C. Wentrup, J. Am. Chem. Soc. 2011, 133, 5413. | CrossRef | CAS |
[9]
C. Wentrup, Top. Curr. Chem. 1976, 62, 173. | CrossRef | CAS |
[10]
S. V. Chapyshev, A. Kuhn, M. W. Wong, C. Wentrup, J. Am. Chem. Soc. 2000, 122, 1572. | CrossRef | CAS |
[11]
C. Addicott, M. W. Wong, C. Wentrup, J. Org. Chem. 2002, 67, 8538. | CrossRef | CAS |
[12]
C. Wentrup, W. D. Crow, Tetrahedron 1970, 26, 4915. | CrossRef | CAS |
[13]
D. Kvaskoff, U. Mitschke, C. Addicott, P. Bednarek, J. Finnerty, C. Wentrup, Aust. J. Chem. 2009, 62, 275. | CrossRef | CAS |
[14]
M. Vosswinkel, H. Lüerssen, D. Kvaskoff, C. Wentrup, J. Org. Chem. 2009, 74, 1171. | CrossRef | CAS |
[15]
(a)
J. M. Berson, in Diradicals (Ed. W. T. Borden) 1982 (Wiley: New York, NY) (b)
D. A. Dougherty, in Kinetics and Spectroscopy of Carbenes and Biradicals (Ed M. S. Platz) 1990 (Plenum: New York, NY)
[16]
D. Kvaskoff, P. Bednarek, L. George, S. Pankajakshan, C. Wentrup, J. Org. Chem. 2005, 70, 7947. | CrossRef | CAS |
[17]
S. Torker, Diploma Thesis: Rearrangements of 2-Pyrimidylnitrene and 3-Pyridazinylnitrene. Ring Expansion and Ring Cleavage 2003 (The University of Queensland, Australia, and Technical University Graz, Austria).
[18]
M. Kuzaj, H. Lüerssen, C. Wentrup, Angew. Chem. Int. Ed. Engl. 1986, 25, 480. | CrossRef |
[19]
(a) C. Wentrup, H.-W. Winter, J. Am. Chem. Soc. 1980, 102, 6159.. | CrossRef | (b)
C. Wentrup, Gas Phase and Matrix Studies, in Azides and Nitrenes (Ed. E. F. V. Scriven) 1984, Chapter 8, pp. 395–433 (Academic Press: Orlando, FL).
[20]
C. Wentrup, C. Thetaz, R. Gleiter, Helv. Chim. Acta 1972, 55, 2633. | CrossRef | CAS |
[21]
C. Addicott, A. Reisinger, C. Wentrup, J. Org. Chem. 2003, 68, 1470. | CrossRef | CAS |
[22]
C. Addicott, H. Lüerssen, M. Kuzaj, D. Kvaskoff, C. Wentrup, J. Phys. Org. Chem. 2011, 24, 999. | CrossRef | CAS |
|
|
 |
Subscriber Login |
 |
|
e-Alerts
Connect with us
