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Synthesis of sulfinates and sulfinic acids
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Recent Literature
Alkyl arenesulfinates and S-thiosulfinates are readily prepared in good
yields by the reaction of sulfinic acids and alcohols or thiols, respectively,
in the presence of lanthanide(III) triflates as catalysts.
J. Drabowicz, M. Kwiatkowska, P. Kiełbasiński, Synthesis, 2008,
3563-3546.
The reaction of p-toluenesulfinic acid with 1,1′-carbonyldiimidazole
(CDI) provides sulfinylimidazoles. The process spontaneously releases carbon
dioxide upon addition of CDI to the acid suggesting the rapid formation of the
proposed reagent. A subsequent reaction with a series of alcohols (primary,
secondary, and tertiary) affords the corresponding sulfinate alkyl esters in
very good yields.
J. L. Shaw, B. J. Austermuehle, J. M. Witte, T. R. Dorsey, C. Delach, C. G.
Hamaker, S. R. Hitchcock, Synthesis, 2021, 53,
2693-2701.
An electrochemical oxidative coupling of thiophenols and alcohols provides
sulfinic esters in the presence of O2 (air) as the oxygen source
smoothly at room temperature.
H. Zhou, J. Duan, D. Xie, J. Yang, B. Ma, G. Wang, C. Wu, X.-C. Wang, Synthesis, 2020, 52,
2705-2712.
A simple and efficient method for converting methyl sulfones to sulfinic acids
involves alkylation with a benzylic halide, followed by in situ elimination of
the resulting styrene in the presence of excess base to yield a sulfinic acid in
a single reaction process.
D. R. Gauthier, Jr., N. Yoshikawa, Org. Lett.,
2016, 18, 5994-5997.
Sulfoxides bearing a tert-butyl group can be activated using N-bromosuccinimide
(NBS) under acidic conditions. Subsequent treatment with various nitrogen,
carbon, or oxygen nucleophiles affords a wide range of sulfinic acid amides, new
sulfoxides, and sulfinic acid esters.
J. Wei, Z. Sun, Org. Lett.,
2015,
17, 5396-5399.
Heterocyclic thioethers and sulfones serve as readily available
precursors for a convenient synthesis of α-chiral sulfinates. Treatment of the sulfinates with hydroxylamine sulfonate in
aqueous solution provides α-C-chiral primary sulfonamides in good yield with retention of stereochemical purity.
M. G. Johson, M. W. Gribble Jr., J. B. Houze, N. A. Paras, Org. Lett., 2014,
16, 6248-6251.
A mild, late-stage conversion of primary sulfonamides to several other
functional groups occurs via initial reductive deamination of sulfonamides to
sulfinates via an NHC-catalyzed reaction of transiently formed N-sulfonylimines.
This method tolerates common functional groups, as exemplified by the late-stage
derivatization of several complex pharmaceutical compounds.
P. S. Fier, K. M. Maloney, J. Am. Chem. Soc.,
2019,
141, 1441-1445.
Sulfinyl transfer agents based on cinchona alkaloids quinine and quinidine as
chiral auxiliaries have been developed.
B. Z. Lu, F. Jin, Y. Zhang, X. Wu, S. A. Wald, C. H. Senanayake, Org. Lett., 2005, 7, 1465-1468.
Related
An oxidation-free method provides sulfinic acids and sulfinate salts from easily
prepared sulfone-substituted benzothiazole derivatives under mild reaction
conditions. One-pot syntheses of sulfones and sulfonamides are also described.
J. J. Day, D. L. Neill, S. Xu, M. Xian, Org. Lett.,
2017, 19, 3819-3822.