Stable cysteine sulfenic acid: synthesis by direct oxidation of a thiol, crystallographic analysis, and elucidation of reactivities

Figures & data

Scheme 1. Redox processes involving cysteine sulfenic acids.

Scheme 2. Facile dehydrative self-condensation of a sulfenic acid to produce a thiosulfinate.

Figure 1. Examples of isolable non-cysteinyl R–SOH. Thermodynamically stabilized compound (1)^[17] and kinetically stabilized ones (2,^[8] 3,^[13] and 4^[15]).

Figure 2. Cavity-shaped substituents, Bpq and Bps groups.

Figure 3. Cradled cysteine model for stabilization of cysteine-derived reactive intermediates such as Cys–SOH.

Scheme 3. Comparison of the thermal stability of BpqCH₂–SeOH (5) and BpsCH₂–SeOH (8).

Scheme 4. Preparation of Cys–SH 12.

Scheme 5. Synthesis of Cys–SOH 13 by H₂O₂ oxidation of Cys–SH 12.

Figure 4. Crystal structure of Cys–SOH 13: (a) stick representation (hydrogen atoms of the Bpsc group are omitted for clarity), and (b) space-filling representation.

Scheme 6. Reaction of Cys–SOH 13 with thiol 14. The yields of 15 were estimated by no-D ¹H NMR spectroscopy utilizing 1,3,5-trimethoxybenzene as an internal standard.

Scheme 7. Reduction of Cys–SOH 13 to Cys-SH 12.

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