Synthesis of aryl sulfides and diaryl sulfides

Name Reactions

Two Steps:

Leuckart Thiophenol Reaction

Recent Literature

A general palladium-catalyzed reaction using the CyPF-t-Bu ligand for the coupling of aryl halides and sulfonates with thiols exhibits extraordinary turnover numbers and high tolerance of functional groups.
M. A. Fernández-Rodríguez, Q. Shen, J. F. Hartwig, J. Am. Chem. Soc., 2006, 128, 2180-2181.

A versatile and efficient Pd(OAc)₂/1,1'-bis(diisopropylphosphino)ferrocene-catalyzed cross-coupling of thiols with aryl halides was developed. Aryl bromides and chlorides can be coupled to aliphatic and aromatic thiols - the widest substrate scope of any reported to date. This catalyst system also enables the coupling of secondary phosphines with aryl halides.
M. Murata, S. L. Buchwald, Tetrahedron, 2004, 60, 7397-7403.

A convenient method for C-S cross-coupling of aryl bromides with various thiols involves the use of a 1,1′-bis(diphenylphosphino)ferrocene (DPPF)-ligated palladium complex with N,N-diisopropylethylamine (DIPEA) as the base. This coupling tolerates a wide range of functional groups, including hydroxy, amino, cyano, nitro, formyl, and carboxyl groups.
T. Okauchi, K. Kuramoto, M. Kitamura, Synlett, 2010, 2891-2894.

A cobalt-catalyzed coupling of aryl halides with thiophenols and alkanethiols allows the preparation of various aryl sulfides in excellent yields under mild reaction conditions.
Y.-C. Wong, T. T. Jayanth, C.-H. Cheng, Org. Lett., 2006, 8, 5613-5616.

Y.-C. Wong, T. T. Jayanth, C.-H. Cheng, Org. Lett., 2006, 8, 5613-5616.

In an efficient Cu-catalyzed one-pot approach for the synthesis of unsymmetrical diaryl thioethers through a Cu-catalyzed double arylation, the aryl thiols are generated in situ from an easily available xanthate and aryl halides. This strategy was further successfully utilized for the synthesis of symmetrical diaryl thioethers, aryl alkyl thioethers, and benzothiazoles.
D. J. C. Prasad, G. Sekar, Org. Lett., 2011, 13, 1008-1011.

cis-1,2-Cyclohexanediol is an efficient and versatile bidentate O-donor ligand that provides a highly active Cu-catalytic system for cross-coupling reactions of alkyl, aryl, or heterocyclic thiols with either alkyl, aryl, heterocyclic, or substituted vinyl halides. This new catalytic system promoted the mild and efficient stereo- and regiospecific synthesis of biologically important vinyl sulfides.
M. S. Kabir, M. Lorenz, M. L. V. Linn, O. A. Namjoshi, S. Ara, J. M. Cook, J. Org. Chem., 2010, 75, 3626-3643.

An efficient ligand-free Cu₂O-catalyzed C-S bond-formation reaction allows the assembling of a large number of diaryl sulfides and alkylaryl sulfides in good yields.
H.-J. Xu, X.-Y. Zhao, Y. Fu, Y.-S. Feng, Synlett, 2008, 3046-3052.

An aryl-sulfur bond formation between aryl iodides and thiophenols is catalyzed by a low amount of readily available and ligand-free copper iodide salt. Various diaryl thioethers are synthesized under relatively mild reaction conditions with good chemoselectivity and functional group tolerance.
E. Sperotto, G. P. M. van Klink, J. G. de Vries, G. van Koten, J. Org. Chem., 2008, 73, 5625-5628.

Indium tri(organothiolate) derivatives are effective nucleophilic coupling partners in Pd-catalyzed C-S crosscoupling reactions to produce functionalized sulfides in excellent yields with high atom efficiency and complete regio- and chemoselectivity.
J.-Y. Lee, P. H. Lee, J. Org. Chem., 2008, 73, 7413-7416.

Rongalite promotes a smoth, one-pot synthesis of aryl alkyl sulfides from disulfides and alkyl halides at room temperature. This protocol is metal-free, strong-base-free, and offers mild reaction conditions, operational simplicity, short reaction times and high yields of products.
R.-y. Tang, P. Zhong, Q.-l. Lin, Synthesis, 2007, 85-91.

Unsymmetrical diorgano-monosulfides, selenides, and tellurides can be synthesized by the coupling of dichalcogenides with aryl- or alkylboronic acids using a copper catalyst in air. The present reaction takes advantage of both organochalcogenide groups on the dichalcogenide.
N. Taniguchi, J. Org. Chem., 2007, 72, 1241-1245.

1,1,1-Tris(hydroxymethyl)ethane as a New, Efficient, and Versatile Tripod Ligand for Copper-Catalyzed Cross-Coupling Reactions of Aryl Iodides with Amides, Thiols, and Phenols
Y.-J. Chen, H.-H. Chen, Org. Lett., 2006, 8, 5609-5612.

A mild, palladium-free method for C-S-bond formation is reported. The standard protocol gave aryl sulfides in excellent yields from thiols and iodides.
C. G. Bates, R. K. Gujadhur, D. Venkataraman, Org. Lett., 2002, 4, 2803-2806.

A nickel-catalyzed alkyl- or arylthiolation of aryl iodides with disulfides allows the preparation of various aryl sulfides. The in situ generated Ni(0)-bpy complex converts ArI into ArSR under neutral conditions. Furthermore, this system enables the use of only 0.5 eq. (RS)₂.
N. Taniguchi, J. Org. Chem., 2004, 69, 6904-6906.

The anti-Markovnikov addition of thiols to alkenes using CeCl₃ as catalyst leads to products in very good yields. The reaction occurred under solvent-free conditions at room temperature.
C. C. Silveira, S. R. Mendes, F. M. Líbero, Synlett, 2010, 790-792.

A highly selective anti-Markovnikov addition of thiols to unactivated alkenes in water at room temperature without any additive is a very simple and efficient method for the synthesis of linear thioethers.
B. C. Ranu, T. Mandal, Synlett, 2007, 925-928.

A cinchona alkaloid-derived urea is an efficient organocatalyst for catalyzing enantioselective conjugate addition between thiols and various α,β-unsaturated ketones to provide optically active sulfides with high chemical yields and enantiomeric excess. The reaction was performed with 0.1 mol % of catalyst in toluene at room temperature.
N. K. Rana, S. Selvakumar, V. K. Singh, J. Org. Chem., 2010, 75, 2089-2091.

A rapid conjugate addition of thiols to α,β-unsaturated ketones is achieved in a hydrophobic ionic liquid [bmim]PF₆/H₂O solvent system in the absence of any acid catalyst. This mild and neutral method gave the corresponding Michael adducts in high yields with excellent 1,4-selectivity. The ionic liquid can be reused.
J. S. Yadav, B. V. S. Reddy, G. Baishya, J. Org. Chem., 2003, 68, 7098-7100.

CeCl₃ • 7H₂O/NaI supported on neutral alumina (Al₂O₃) promotes heteroatom Michael additions under solvent-free conditions. The CeCl₃ • 7H₂O/NaI/Al₂O₃ system works well for hetero-Michael additions of weak nucleophiles such as imidazoles and carbamates to various acceptors.
G. Bartoli, M. Bartolacci, A. Giuliani, E. Marcantoni, M. Massaccesi, E. Torregiani, J. Org. Chem., 2005, 70, 169-174.

A mild, versatile, palladium-free method for the synthesis of vinyl sulfides using the soluble copper(I) catalyst [Cu(phen)(PPh₃)₂]NO₃ is reported. The desired vinyl sulfides are obtained with retention of stereochemistry in good to excellent yields.
C. G. Bates, P. Saejueng, M. Q. Doherty, D. Venkataraman, Org. Lett., 2004, 6, 5005-5008.

An efficient, mild and transition-metal-free N-arylation of amines, sulfonamides, and carbamates and O-arylation of phenols and carboxylic acids has been achieved by using various o-silylaryl triflates in the presence of CsF.
Z. Liu, R. C. Larock, J. Org. Chem., 2006, 71, 3198-3209.

A new synthetic method for the preparation of potassium organotrifluoroborates through nucleophilic substitution of potassium bromo- and iodomethyltrifluoroborates is described. Potassium halomethyltrifluoroborates have been prepared via in situ reaction of n-BuLi with dibromo- and diiodomethane, respectively, in the presence of trialkyl borates, followed by treatment with KHF₂.
G. A. Molander, J. Ham, Org. Lett., 2006, 8, 2031-2034.

A regio and anti-selective copper-catalyzed 1,2-hydroxysulfenylation of alkenes can be carried out by the use of disulfides and acetic acid. Reoxidation of intermediate sulfides by oxygen enables the use of both organosulfide groups of the disulfides.
N. Taniguchi, J. Org. Chem., 2006, 71, 7874-7876.