Abstract
Alkene aziridination by azides through uncatalyzed thermal gas phase routes has been studied using the DFT B3LYP/6-31G(d,p) method, where the possible role of discrete nitrene intermediates is emphasized. The thermal decomposition of azides is studied using the MP2/aug-cc-pVDZ strategy as well. The MP2 (but not the B3LYP) results discount the existence of singlet alkylnitrenes where the alkyl group has an α-hydrogen. Addition of the lowest lying singlet and triplet nitrenes R-N (R = H, Me, Ac) to four different alkene substrates leading to aziridine formation was studied by the B3LYP method. Singlet nitrenes with alkenes can yield aziridines via a concerted mechanism, where H-N insertion takes place without a barrier, whereas Me-N shows larger barriers than Ac-N. Methyl substitution in the alkene favors this reaction. Triplet nitrene addition to alkenes is studied as a two-step process, where the initially formed diradical intermediates cyclize to form aziridines by ISC (intersystem crossing) and collapse. Scope for C-C bond rotation in the diradical leads to loss of stereochemical integrity for triplet nitrene addition to cis- and trans-2-butenes. Geometries of the transition states in the various reaction steps studied here are described as “early” or “late” in good accordance with the Hammond postulate.
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Acknowledgments
The authors thank the Council of Scientific and Industrial Research, Govt. of India, for computational facilities received through a sponsored research project. S.P.D. thanks the University Grants Commission, New Delhi, for financial assistance through the UGC Research Fellowship for Meritorious Students.
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Optimized geometries (in Cartesian coordinates) of the molecules studied here are given in the Supplementary Information which is available at www.ias.ac.in/chemsci.
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DEVI, S.P., SALAM, T. & DUNCAN LYNGDOH, R.H. Uncatalyzed thermal gas phase aziridination of alkenes by organic azides. Part I: Mechanisms with discrete nitrene species. J Chem Sci 128, 681–693 (2016). https://doi.org/10.1007/s12039-016-1073-5
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DOI: https://doi.org/10.1007/s12039-016-1073-5