Abstract
To enhance the versatility of organic azides in organic synthesis, a better understanding of their photochemistry is required. Herein, the photoreactivity of azidoisoxazole 1 was characterized in cryogenic matrices with IR and UV-Vis absorption spectroscopy. The irradiation (λ = 254 nm) of azidoisoxazole 1 in an argon matrix at 13 K and in glassy 2-methyltetrahydrofuran (mTHF) at 77 K yielded nitrosoalkene 3. Density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations were used to aid the characterization of nitrosoalkene 3 and to support the proposed mechanism for its formation. It is likely that nitrosoalkene 3 is formed from the singlet excited state of azidoisoxazole 1 via a concerted mechanism or from cleavage of an intermediate singlet nitrene that does not undergo efficient intersystem crossing to its triplet configuration.
Highlights
Organic azides are one of the most versatile functional groups in synthesis, as they can be used to form new C–N bonds, either through electrophilic or nucleophilic substitution [1]
We report the photoreactivity of azidoisoxazole 1 in cryogenic argon and
To determine the photoreactivity of azidoisoxazole 1 at cryogenic temperatures, it was deposited into an argon matrix at 13 K and irradiated with a 254 nm UV pen
Summary
Organic azides are one of the most versatile functional groups in synthesis, as they can be used to form new C–N bonds, either through electrophilic or nucleophilic substitution [1]. Their dipolar character makes them useful for forming new C–N bonds through cycloaddition. The Huisgen 1,3-dipolar cycloaddition of organic azides to alkynes is commonly used to form triazole compounds, which have utility in medicinal and pharmaceutical chemistry [2,3,4]. Better insight into the photoreaction mechanisms of organic azides will undoubtedly aid in their use in synthetic applications [6]
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