Categories: S-S Bond Formation >
Synthesis of Disulfides
The reaction of a thiol with 1-chlorobenzotriazole (BtCl) affords the benzotriazolated thiol (RSBt) without appreciable formation of the symmetrical disulfide. RSBt reacts with another thiol to form the unsymmetrical disulfide in a one-pot sequence without the need for toxic and harsh oxidizing agents.
R. Hunter, M. Caira, N. Stellenboom, J. Org. Chem., 2006, 71, 8268-8271.
Unsymmetrical disulfides have been prepared from the corresponding thiols and bis-(5,5-dimethyl-2-thiono-1,3,2-dioxaphosphorinanyl)disulfide under mild conditions with very good yields. This method can be applied to thiols bearing neutral, aromatic, basic or acidic functionalities with variable length of carbon chain.
S. Antoniow, D. Witt, Synthesis, 2007, 363-366.
A convenient method for the synthesis of unsymmetrical disulfides under mild conditions in good to excellent yields is based on the use of a readily available organophosphorus sulfenyl bromide as activating agent. The unsymmetrical disulfides can be obtained for l-cysteine derivatives and thiols bearing neutral, basic, or acidic functionalities.
M. Szymelfejnik, S. Demkowicz, J. Rachon, D. Witt, Synthesis, 2007, 3528-3534.
The reaction of aryl halides with ethyl potassium xanthogenate in the presence of MOF-199 provides O-Ethyl-S-aryl carbonodithioates as intermediates, that can be converted into symmetrical diaryl disulfides, unsymmetrical aryl alkyl(aryl′) disulfides by the reaction with S-alkyl(aryl) sulfurothioates (Bunte salts) as well as unsymmetrical aryl alkyl(aryl′) sulfides.
M. Soleiman-Beigi, Z. Arzehgar, Synlett, 2018, 29, 986-992.
N-Trifluoroacetyl arenesulfenamides are effective precursors for the synthesis of unsymmetrical disulfides and sulfenamides. Reactions of N-trifluoroacetyl arenesulfenamides with thiols and amines gave the desired products in high yields within short reaction times.
M. Bao, M. Shimizu, Tetrahedron, 2003, 59, 9655-9659.
The use of sodium in silica gel enables an efficient synthesis of symmetrical disulfanes from organic thiocyanates at room temperature. This protocol provides an attractive alternative to existing methods for the preparation of symmetrical disulfanes as it avoids the use of foul-smelling thiols.
C. K. Maurya, A. Mazumder, A. Kumar, P. K. Gupta, Synlett, 2016, 27, 409-411.
An organodiselenide catalyzed the aerobic oxidation of thiols into disulfides in practical yields without any reagents/additives, base, and light source. The synthesized diselenide also catalyzes the reduction of hydrogen peroxide into water.
V. Rathore, A. Upadhyay, S. Kumar, Org. Lett., 2018, 20, 6274-6278.
Thiols were effectively oxidized into disulfides by reacting with hydrogen peroxide in the presence of a catalytic amount of iodide ion or iodine.
M. Kirihara, Y. Asai, S. Ogawa, T. Noguchi, A. Hatano, Y. Hirai, Synthesis, 2007, 3286-3289.
Selective and quantitative conversion of thiols to disulfides was effected by dimethyl sulfoxide under mild conditions catalyzed by dichlorodioxomolybdenum(VI).
R. Sanz, R. Aguado, M. R. Pedrosa, F. Arnáiz, Synthesis, 2002, 856-858.
A mild and efficient oxidation of various thiols affords the corresponding disulfides using 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) as oxidant under both solution and solvent-free conditions.
A. Khazaei, M. A. Zolfigol, A. Rostami, Synthesis, 2004, 2959-2961.