Reactions of Thiiranium and Sulfonium Ions with Alkenes in the Gas Phase

• Published in: Journal of organic chemistry Vol. 84; no. 16; pp. 10076 - 10087
• Main Authors: Brydon, Samuel C, Lim, Shea Fern, Khairallah, George N, Maître, Philippe, Loire, Estelle, da Silva, Gabriel, O’Hair, Richard A. J, White, Jonathan M
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 16.08.2019; Amer Chemical Soc
• Subjects: Analytical chemistry; Chemical Sciences; Chemistry; Chemistry, Organic; Organic chemistry; Physical Sciences; Science & Technology; DENSITY FUNCTIONALS; CARBON; SPECTROSCOPY; EPISELENONIUM ION; SELENIRANIUM IONS; REACTIVITY; SULFENOFUNCTIONALIZATION; TRAP; SUBSTITUTION-REACTIONS; PI-LIGAND EXCHANGE
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.9b01264

Ion–molecule reactions between thiiranium ion 11 (m/z 213) and cyclohexene and cis-cyclooctene resulted in the formation of addition products 17a and 17b (m/z 295 and m/z 323, respectively) via an electrophilic addition pathway. Associative π-ligand exchange involving direct transfer of the PhS+ moiety, which has been observed for analogous seleniranium ions in the gas phase, did not occur despite previous solution experiments suggesting it as a valid pathway. DFT calculations at the M06-2X/def2-TZVP level of theory showed high barriers for the exchange reaction, while the addition pathway was more plausible. Further support for this pathway was provided with Hammett plots showing the rate of reaction to increase as the benzylic position of thiiranium ion derivatives became more electrophilic (ρ = +1.69; R 2 = 0.974). The more reactive isomeric sulfonium ion 22 was discounted as being responsible for the observed reactivity with infrared spectroscopy and DFT calculations suggesting little possibility for isomerization. To further explore the differences in reactivity, thiiranium ion 25 and sulfonium ion 27 were formed independently, with the latter ion reacting over 260 times faster toward cis-cyclooctene than the thiiranium ion rationalized by calculations suggesting a barrierless pathway for sulfonium ion 27 to react with the cycloalkene.