C-S Cross-coupling

R3 R1 HN rS fluorous Suzuki C-C or fluorous thiol C-S cross-coupling R1 R3 HN R2... 

Molander, G. A., Yun, C.-S. Cross-coupling reactions of primary alkylboronic acids with aryl triflates and aryl halides. Tetrahedron 2002, 58, 1465-1470. 

Fluorous Suzuki C-C or Fluorous Thiol C-S Cross Coupling... 

Route 1 involves an initial migratory arylzincation pathtvay that is followed by a copper-mediated reaction with elemental sulfur, with accompanying C-S cyclization to afford a substituted benzothiophene in a one-pot reaction. Alternatively, in route 2, the zinc intermediate is first trapped by iodine, and subsequent copper-catalyst allows C-S/C-Se bond formation followed by cyclization in the presence of elemental sulfur or selenium to afford the corresponding benzochalcogenophene. A modular two-step synthesis of dithieno[3,2-l) 2, 3 -d]thiophene derivatives by C-S cross-coupling and oxidative dehydro C-H coupHng was also described in the year 2014 (14OL4086). 

Bhong, B. Y., Shelke, A. V., and Karade, N. N. 2013. Nano copper oxide mediated Ugand-free C-S cross-coupling and concomitant oxidative aromatization of 4-aryl-3,4-dihydropy-rimidin-2(l//)-thione with diaryUodonium salts. Tetrahedron Lett. 54(8) 739-743. 

Surprisingly, the phospine oxide f-Bu2P(0)H suggested by Li et al. was found to be an efficient ligand for the C—S cross-coupling reaction, which made it possible to carry out the reaction at 110 °C, even with unactivated aryl chlorides (Scheme 3.8) [20, 21]. 

The Pd-catalyzed C—S cross-coupling reaction was carried out starting with aryl bromides and aryl triflates and potassium thioacetate (Scheme 3.17) [43]. Various sulfur compounds (such as ArSH, ArSR, ArSCl, ArSOCl) can be obtained from these products in a single step. 

Pincer complexes of nickel (PCP)NiCl were reported as efficient catalysts for the C—S cross-coupling reaction (Scheme 3.24). With the exception of R= Bu, high product yields were observed [51]. The involvement of Ni(I) and Ni(III) complexes in the mechanism of the catalytic cycle was proposed for this particular case. 

A soluble Cu(I) complex has been successfully used by Venkataraman et al. in C—S cross-coupling when more reactive vinyl iodides were utilized as a reagent (Scheme 3.30) [61],... 

The catalytic system based on Cul and N,N-dimethylglycine ligand was found to catalyze C S cross-coupling of aryl iodides and vinyl bromides with sodium dithiocarbamates (Scheme 3.49) [87]. As in the previous case, PhBr did not react... 

The use of nanoparticle for the C—S cross-coupling has been reported under ligand-free conditions. Punniyamurthy and coworkers introduced air-stable CuO nanoparticles for the coupling of thiols with aryl iodides [102, 172]. Karvembu [173] and Kakulapati [174] subsequently employed CuO nanoparticles for the coupling of aryl halides with thiophenol and ethyl potassium xanthogenate, respectively. Kamal and coworkers used CuO nanoparticles/graphene oxide for the coupling of aryl chlorides with thiols (Scheme 20.56) [175]. 

In 2008, Bolm s group [136] reported the Fe-catalyzed C-S cross-couplings of thiols with aryl iodides. The reactions were conducted using FeClj (10 mol%), DMEDA (20 mol%), and NaOtBu (2 equiv) in toluene at 135 °C for 24h. The reaction scope and functional group compatibility were successfully demonstrated and the yields were generally very good. 

C S cross-coupling reactions, where benzothiazole intermediates were further transformed to arylsulfides 139 under intermolecular C—S cross-coupling reaction conditions. In 2010, Pan et al. selectively synthesized 2-(phenylihio)phe-nols 142 via a tandem C S coupling and C H functionalization employing a copper catalyst system. The reaction mechanism, based on an isotope labeled strategy, revealed that dimethyl sulfoxide served as a main oxidant in the C H oxidation step 143. 

Ranjit S, Duan Z, Zhang P, Liu, X. Synthesis of vinyl sulfides by copper-catalyzed decarboxylative C—S cross-coupling. Org. Lett. 2010 12 4134- 136. 

Duan Z, Ranjit S, Zhang P, Liu X. Synthesis of aryl sulfides by decarboxylic C—S cross-couplings. Chem. Eur. J. 2009 15 3666-3669. 

Ramana T, Sha P, Das M, Punniyamurthy T. Copper-catalyzed domino intra and intermolecular C—S cross-coupling reactions synthesis of 2-(arylthio)arylcyanamides. Org. Lett. 2010 12 84-87. 

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