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CC BY-NC-ND 4.0 · SynOpen 2021; 05(01): 91-99
DOI: 10.1055/a-1422-9411
DOI: 10.1055/a-1422-9411
psp
Simple and Efficient Synthesis of Allyl Sulfones through Cs2CO3-Mediated Radical Sulfonylation of Morita–Baylis–Hillman Adducts with Thiosulfonates
We thank the Department of Science & Technology - Promotion of University Research and Scientific Excellence (DST-PURSE; SR/PURSE Phase 2/32/G) and the Council of Scientific and Industrial Research (CSIR-EMR-II; 02(0340)/18/EMR-II) for funding support. A.S. and M.W. thank CSIR-SRF and UGC-SRF, respectively, for their Research Fellowships.
Abstract
A highly efficient and eco-friendly method has been developed for the synthesis of allyl sulfones using Morita–Baylis–Hillman (MBH) adducts and thiosulfonates under mild conditions. The Cs2CO3-promoted radical sulfonylation provided a series of allyl sulfones in good to high yields with high stereoselectivities. A wide variety of MBH bromides/acetates as well as thiosulfonates were tolerated and reliable in scaled-up synthesis. A plausible mechanism is proposed to rationalize the radical sulfonylation.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1422-9411.
- Supporting Information
Publication History
Received: 16 February 2021
Accepted after revision: 08 March 2021
Accepted Manuscript online:
10 March 2021
Article published online:
29 March 2021
© 2021. This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial-License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)
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Recent leading articles:
For homolytic cleavage of thiosulfonates in EPR studies, see:
For thiosulfonylation of alkenes and alkynes, see:
For sulfonylation of MBH adducts using sodium sulfinates, see:
For sulfonylation of MBH adducts using other sulfonyl agents, see:
For selected reviews on MBH reaction, see:
For reviews of thiyl radicals in organic synthesis, see:
The mixture of Z/E isomers of allyl sulfones was based on the corresponding MBH allyl bromides, see:
In the 1H NMR spectra of aryl substituted products, the vinylic proton cis- to the ester group appears around δ = 7.90 ppm and around δ = 6.85 ppm for the Z- and E-isomers, respectively. Similarly, the vinylic proton of the major Z-isomer appears at around δ = 7.09 ppm and a minor peak for the E-isomer appears at around δ = 6.08 ppm for alkyl substituted products. See: