Abstract
The reactions of methylsulfonylnitrene 1a and trifluoromethylsulfonylnitrene 1b with acetylene 2, dimethylacetylene 3, acetylenedicarboxylic acid 4, hydrogen cyanide 5, acetonitrile 6, cyanoformic acid 7 were studied theoretically at the CBS-QB3 level of theory. The main products of the reaction of triplet sulfonylnitrenes 31 with alkynes 2–4 are 1,2,3-oxathiazole 2-oxides 10 formed from triplet diradical adducts after intersystem crossing (ISC) to their singlet spin-isomers. Products 10 are also formed from singlet nitrenes 11 along with N-vinylidenesulfonamides 9 and 1-(alkylsulfonyl)-1Н-azirines 11. The latter, being antiaromatic, isomerize exothermically to 2-(alkylsulfonyl)-2Н-azirines 12. In a similar way, both singlet and triplet sulfonylnitrenes 1 react with nitriles 5–7 to give 1-(alkylsulfonyl)-1H-diazirines 16. With singlet nitrenes, nitriles 5–7 can also react with the formation of 2-(methylidyne)-1-(alkylsulfonyl)diazan-2-ium-1-ides 14, which undergo either intramolecular 1,3-cyclization to 3-(alkylsulfonyl)-3H-diazirines 17 or intramolecular 1,5-cyclization to 1,2,3,4-oxathiadiazole 2-oxides 15. Relative stability of the key products and activation barriers of their interconversion are discussed.
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