m‐CPBA/KOH: An Efficient Reagent for Nucleophilic Epoxidation of gem‐Deactivated Olefins.

Ruano, José Luis Garcı́a; Fajardo, Cristina; Fraile, Alberto; Martı́n, M. Rosario

doi:10.1002/chin.200543055

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“…Only the tris(dimethylamino)sulfoxonium was successfully synthesized using this approach. Since m-chloroperoxybenzoate can be used to oxidize electronpoor olefins in CH 2 Cl 2 , 53 we attempted to oxidize the [S(NR 2 ) 3 ][PF 6 ] salts in organic solvents. Though oxidation in pure CH 2 Cl 2 was incomplete, oxidization could be accomplished essentially quantitatively using excess mCPBA/ K 2 CO 3 in a 1:1 mixture of CH 2 Cl 2 :hexanes.…”

Section: ■ Introductionmentioning

confidence: 99%

Examining the Alkaline Stability of Tris(dialkylamino)sulfoniums and Sulfoxoniums

et al. 2022

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Herein, a synthetic method was developed to prepare a series of tris(dialkylamino)sulfonium and sulfoxonium cations from sulfur monochloride. Alkaline stability studies of these two cation families in 2 M KOH/CD 3 OH solution at 80 °C revealed how degradation pathways change as a function of the oxidation state of the S center, as determined by 1 H NMR spectroscopy. The sulfonium cations ( + S(NR 2 ) 3 ) typically degrade by nucleophilic attack at the sulfur atom with loss of an amino group and a proton transfer reaction to produce sulfoxides, while the sulfoxoniums ( + O�S(NR 2 ) 3 ) tend to degrade by loss of an R group to form sulfoximines. From the group of sulfoniums and sulfoxoniums explored in this work, the tris(piperidino)sulfoxonium cation was noted to have excellent alkaline stability. This sulfoxonium should be suitable for future examination as a tethered cation in anion-exchange membranes (AEMs), or as a phase-transfer catalyst in biphasic reactions.

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Section: ■ Introductionmentioning

confidence: 99%