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

Samuel C Brydon; Shea Fern Lim; George N Khairallah; Philippe Maitre; Estelle Loire; Gabriel da Silva; Richard AJ O'Hair; Jonathan M White

Journal article

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

Samuel C Brydon, Shea Fern Lim, George N Khairallah, Philippe Maitre, Estelle Loire, Gabriel da Silva, Richard AJ O'Hair, Jonathan M White

The Journal of Organic Chemistry | American Chemical Society | Published : 2019

DOI: 10.1021/acs.joc.9b01264

Abstract

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 o..

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University of Melbourne Researchers

Gabriel da Silva Author

Richard O'Hair Author

Jonathan White Author

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Grants

Awarded by Australian Research Council

Awarded by European Community

Funding Acknowledgements

We thank the Australian Research Council for the financial support (DP0770565 to JMVV and DP180101187 to RAJO), the Australian Government for a Research Training Program (RTP) scholarship for S.B., and The University of Melbourne for the Melbourne Research Scholarship (MRS) for S.F.L. Financial support from the European Community's Horizon 2020 Programme CALIPSOplus (grant no. 730872) is gratefully acknowledged. The HRMS spectra were acquired at the Mass Spectrometry and Proteomics Facility (MSPF), Bio21 Institute, The University of Melbourne. The DFT calculations were performed on the Spartan High Performance Computing (HPC) System hosted by Research Platform Services at The University of Melbourne.<SUP>70</SUP>