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. 2017 Mar 1;8(3):2175-2178.
doi: 10.1039/c6sc04480h. Epub 2016 Dec 7.

CO/O2 assisted oxidative carbon-carbon and carbon-heteroatom bond cleavage for the synthesis of oxosulfonates from DMSO and olefins

Ailong Shao  1   2 , Meng Gao  1 , Songtao Chen  1 , Tao Wang  1 , Aiwen Lei  1   2
Affiliations

CO/O2 assisted oxidative carbon-carbon and carbon-heteroatom bond cleavage for the synthesis of oxosulfonates from DMSO and olefins

Ailong Shao et al. Chem Sci. .

Abstract

Selective carbon-carbon and carbon-heteroatom bond cleavage was achieved in a one reaction system. With this strategy a novel Pd/Cu-catalyzed aerobic oxidative oxosulfonation of olefins with DMSO has been developed. Preliminary mechanistic investigations indicated that CO/O2 assisted the bond cleavage and the leaving groups from the starting materials were trapped by O2 and underwent a hydroxylation process.

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Figures

Scheme 1
Scheme 1. The synthesis of oxosulfonates via C–C/C–S bond cleavage.
Scheme 2
Scheme 2. The reaction between ethene-1,1-diyldibenzene and dimethyl sulfoxide.
Scheme 3
Scheme 3. Reactions of alkenes 4 and dimethyl sulfoxide 2. Reaction conditions: 4 (0.20 mmol), 2 (1 mL), PdCl2 (10 mol%), Cu(OPiv)2 (20 mol%), d-(–)-fructose (40 mol%) and 1 atm CO/O2 (1 : 1) at 80 °C for 15 h. Isolated yields.
Scheme 4
Scheme 4. Labelling and trapping experiments.
Scheme 5
Scheme 5. Radical inhibiting experiment.
Scheme 6
Scheme 6. Control experiment.
Scheme 7
Scheme 7. Proposed mechanism for C–S and C–C bond cleavage.
Scheme 8
Scheme 8. Acetic acid trapping experiment.
See this image and copyright information in PMC

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