Synthesis of sulfonates

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A new, simple method for the conversion of alcohols to tosylamides is presented.
M. C. Marcotullio, V. Campagna, S. Sternativo, F. Costantino, M. Curini, Synthesis, 2006, 2760-2766.

M. C. Marcotullio, V. Campagna, S. Sternativo, F. Costantino, M. Curini, Synthesis, 2006, 2760-2766.

A direct preparation of O-substituted hydroxylamines from alcohols is described by O-alkylation of tert-butyl N-hydroxycarbamate with the methanesulfonates of respective alcohols, followed by acidic N-deprotection.
S. Albrecht, A. Defoin, C. Tarnus, Synthesis, 2006, 1635-1638.

4-Methylpyridine N-oxide catalyzes an amine-free sulfonylation of various alcohols in the presence of 4Å molecular sieves at room temperature. This mild method gives various sulfonylated products in high yields, and can be applied to base-sensitive substrates.
K. Yoshida, Y. Matsumoto, J. Masuda, S. Kitagaki, Synlett, 2022, 33, 1570-1574.

A facile and efficient indium-catalyzed sulfonylation of amines allows the synthesis of a wide range of sulfonamides in excellent yields. The method showed a generality for substrates including less nucleophilic and sterically hindered anilines, and it is also applicable for preparing sulfonic esters from sulfonyl chlorides and alcohols.
J. Yan, J. Li, D. Cheng, Synlett, 2007, 2442-2444.

Ytterbium(III) trifluoromethanesulfonate efficiently catalyzes the reaction of primary and secondary alcohols with toluenesulfonic acid anhydride to yield the alkyl tosylates in high yields. The reactions were carried out under neutral and mild conditions and product purification was easily achieved by means of short column chromatography.
S. Comagic, R. Schirrmacher, Synthesis, 2004, 885-888.

Electro-oxidation enables a practical and sustainable synthesis of arylsulfonate from stable and readily available phenols and sodium arenesulfinates as the starting materials. The reaction takes place under mild reaction conditions without additional oxidants. A wide range of arylsulfonate esters were produced in good to excellent yields.
Z. Tian, Q. Gong, T. Huang, L. Liu, T. Chen, J. Org. Chem., 2021, 86, 15914-15926.

Two chromatography-free and eco-friendly protocols for tosylation and mesylation of phenols offer simplicity, short reaction time, mild conditions, and environmental friendliness. The reactions transform a broad range of substrates in excellent yields.
X. Lei, A. Jalla, M. A. A. Shama, J. M. Stafford, B. Cao, Synthesis, 2015, 47, 2578-2585.

A mild and efficient interconversion from silyl ethers to sulfonates esters proceeds readily in acetonitrile at room temperature in the presence of p-toluenesulfonyl fluoride and a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7ene (DBU). This method can be used with trimethysilyl (TMS), triethylsilyl (TES) and tert-butyldimethylsilyl (TBDMS) ethers.
V. Gembus, F. Marsais, V. Levacher, Synlett, 2008, 1463-1466.

Treatment of a various aryl methyl ethers with a mixture of phosphorus pentoxide in methanesulfonic acid enables a simple and efficient one-pot demethylation-mesylation reaction to afford the corresponding aryl mesylates in good yields.
B. Kaboudin, Y. Abedi, Synthesis, 2009, 2025-2028.

The nitrophenolate group in 4-nitrophenyl phenylmethanesulfonate can be exchanged for a wide range of (substituted) phenols and alkyl alcohols. Quantitative yields were reached within 10 min under ambient conditions and required only filtering through silica as workup.
A. F. J. van den Boom, M. Subramaniam, H. Zuilhof, Org. Lett., 2022, 24, 8621-8626.

Diarylborinic acid catalysis is an efficient and general method for selective acylation, sulfonylation, and alkylation of 1,2- and 1,3-diols. The efficiency, generality, and operational simplicity of this method are competitive with those of the broadly applied organotin-catalyzed reactions. A mechanism is suggested, in which a tetracoordinate borinate complex reacts with the electrophilic species in the turnover-limiting step of the catalytic cycle.
D. Lee, C. L. Williamson, L. Chan, M. S. Taylor, J. Am. Chem. Soc., 2012, 134, 8260-8267.

Dibutyltin oxide catalyzes a selective and rapid sulfonylation of glycols at the primary alcohol in the presence of stoichiometric p-toluenesulfonyl chloride and triethylamine in CH₂Cl₂. α-Heterosubstituted primary alcohols appeared optimal for best results, supporting the intermediacy of a five-membered chelate.
M. J. Martinelli, N. K. Nayyar, E. D. Moher, U. P. Dhokte, J. M. Pawlak, R. Vaidyanathan, Org. Lett., 1999, 1, 447-450.

Highly stereoselective methods for preparing enol triflates derived from substituted acetoacetate derivatives under Schotten-Baumann-type conditions provide either Z enolate geometry using aqueous LiOH or E using aqueous (Me)₄NOH in combination with triflic anhydride.
D. Babinski, I. Soltani, D. E. Frantz, Org. Lett., 2008, 10, 2901-2904.

1,3-diketones, β-ketoaldehydes, β-ketoesters, β-ketoamides, β-ketophosphonates and β-ketosulfones were efficiently converted to the corresponding Z vinyl triflates with high stereoselectivity. Precoordination with lithium triflate in dichloromethane and enolization with mild bases followed by trapping with triflic anhydride probably accounted for such high selectivity.
S. Specklin, P. Bertus, J.-M. Weibel, P. Pale, J. Org. Chem., 2008, 73, 7845-7848.

α-Substituted β-keto esters undergo (E)-selective enol tosylations with TsCl using Me₂N(CH₂)₆NMe₂ as reagent, whereas the use of TMEDA and LiCl enables (Z)-selective enol tosylations.
Y. Ashida, Y. Sato, A. Honda, H. Nakatsuji, Y. Tanabe, Synthesis, 2016, 48, 4072-4080.

TsCl coupled with NMI forms a highly reactive N-sulfonylammonium intermediate. β-Ketoesters undergo (E)-selective tosylation using TsCl-NMI-Et₃N and (Z)-selective tosylation using TsCl-NMI-LiOH in good yield. Stereoretentive Negishi and Sonogashira couplings using enol tosylates proceed successfully to give trisubstituted α,β-unsaturated esters.
H. Nakatsuji, K. Ueno, T. Misaki, Y. Tanabe, Org. Lett., 2008, 10, 2131-2134.

H. Nakatsuji, K. Ueno, T. Misaki, Y. Tanabe, Org. Lett., 2008, 10, 2131-2134.

An (E)- and (Z)-stereocomplementary preparative method for α,β-disubstituted α,β-unsaturated esters is performed via three general and robust reaction sequences: Ti-Claisen condensation (formylation) of esters to give α-formyl esters, (E)- and (Z)-stereocomplementary enol tosylation using TsCl-N-methylimidazole-Et₃N and LiOH, and stereoretentive Suzuki-Miyaura cross-coupling.
H. Nakatsuji, H. Nishikado, K. Ueno, Y. Tanabe, Org. Lett., 2009, 11, 4258-4261.

H. Nakatsuji, H. Nishikado, K. Ueno, Y. Tanabe, Org. Lett., 2009, 11, 4258-4261.

(E)- or (Z)-trisubstituted α,β-unsaturated esters have been prepared in three steps from N-protected glycine. The key step is the highly selective enol tosylation of γ-amino β-keto esters followed by an effective Suzuki-Miyaura coupling reaction with a variety of aryl boronic acids.
J. Baxter, D. Steinhuebel, M. Palucki, I. W. Davies, Org. Lett., 2005, 7, 215-218.

J. Baxter, D. Steinhuebel, M. Palucki, I. W. Davies, Org. Lett., 2005, 7, 215-218.

A simple and efficient synthesis of aryl triflates under biphasic conditions is described which omits the use of amine bases and allows facile isolation by simple solvent evaporation after phase separation. Good yields can also be obtained without the use of organic solvent.
D. E. Frantz, D. G. Weaver, J. P. Carey, M. H. Kress, U. H. Dolling, Org. Lett., 2002, 4, 4717-4718.

Mild, novel procedures have been developed for the syntheses of aryl halides from the corresponding phenols in modest to good yields via boronate ester intermediates.
A. L. S. Thompson, G. W. Kabalka, M. R. Akula, J. W. Huffman, Synthesis, 2005, 547-550.