Sulfur(IV)-Mediated Transformations: From Ylide Transfer to Metal-Free Arylation of Carbonyl Compounds

Huang, Xueliang; Patil, Mahendra; Farès, Christophe; Thiel, Walter; Maulide, Nuno

doi:10.1021/ja4017683

Cited by 145 publications

(41 citation statements)

References 106 publications

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“…Recently, we34353637383940 and others41424344454647484950515253545556 reported the metal-free, sulfoxide directed57 C–H functionalization of a variety of molecular scaffolds, which was enabled by an interrupted Pummerer reaction28. Spurred on by these recent achievements, we considered the use of benzothiophene S -oxides 1 for the synthesis of important C3-functionalized benzothiophenes, as the corresponding sulfonium salts I and II , formed after reaction with the coupling partners, lack aromaticity about the five-membered ring and should therefore undergo facile C–C bond formation via [3,3]-sigmatropic rearrangement58, thus delivering unexplored reactivity not accessible in benzothiophenes.…”

Section: Resultsmentioning

confidence: 99%

Regioselective synthesis of C3 alkylated and arylated benzothiophenes

et al. 2017

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Benzothiophenes are heterocyclic constituents of important molecules relevant to society, including those with the potential to meet modern medical challenges. The construction of molecules would be vastly more efficient if carbon–hydrogen bonds, found in all organic molecules, can be directly converted into carbon–carbon bonds. In the case of elaborating benzothiophenes, functionalization of carbon–hydrogen bonds at carbon-number 3 (C3) is markedly more demanding than at C2 due to issues of regioselectivity (C3 versus C2), and the requirement of high temperatures, precious metals and the installation of superfluous directing groups. Herein, we demonstrate that synthetically unexplored but readily accessible benzothiophene S-oxides serve as novel precursors for C3-functionalized benzothiophenes. Employing an interrupted Pummerer reaction to capture and then deliver phenol and silane coupling partners, we have discovered a directing group-free method that delivers C3-arylated and -alkylated benzothiophenes with complete regioselectivity, under metal-free and mild conditions.

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Section: Resultsmentioning

confidence: 99%

Regioselective synthesis of C3 alkylated and arylated benzothiophenes

et al. 2017

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“…Huang et al [90] reported the TMF carbon arylation from carbonyl compounds via ylide with sulphur-mediated transformations (Scheme 45). Interestingly, the above protocol leads to irrelevant sulphur biaryl 129 outcomes.…”

Section: Miscellaneous Arylationmentioning

confidence: 99%

Synthetic journey towards transition metal-free arylations

Roopan

Palaniraja

2014

Res Chem Intermed

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In general, aryl-aryl transformations were investigated via transition metal-catalysed reactions. However, transition metal-mediated organic synthesis provided higher yields but has some flaws such as high cost, and the need for careful exclusion of air and moisture during the reactions. Possibly, there may be contamination of the product from traces of heavy metals present. To overcome these kinds of disadvantages, continuous efforts have been focused on the recent development of aryl-aryl formation through transition metal-free (TMF) reactions. However, most of these cross-couplings reaction were limited to hetero and electron-rich arenes which require strong inorganic bases. Our critical review includes a synthetic pathway to prepared X-aryl (X = C, N, O and S) motif by a transition metal-free scenario. Formerly, TMF reactions were carried out by various sources like strong bases, diazodium salt, aryliodonium salt, organo-catalysts and versatile energy sources like microwave heating, visible light and photochemical reactor. In this review, we have focused on the transition metal-free arylations.

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“…4, entries 8–11) because cyclohexanone is structurally more rigid than either cycloheptanone and acyclic aliphatic ketones, which makes cyclohexanone less reactive towards the C−C bond formation414243. The three-component reaction mentioned above provides a convenient access to α-aryl ketones4142444546474849 having a trifluoromethyl group on the aryl ring (Fig. 1)2427 in a single operation505152535455.…”

Section: Resultsmentioning

confidence: 99%

4-Trifluoromethyl-p-quinols as dielectrophiles: three-component, double nucleophilic addition/aromatization reactions

Dong

Shi

Pan

et al. 2016

Sci Rep

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In recent years, numerous methods have emerged for the synthesis of trifluoromethylated arenes based on the late-stage introduction of a trifluoromethyl group onto an aryl ring. In sharp comparison, the synthesis of trifluoromethylated arenes based on the pre-introduction of a trifluoromethyl group onto an “aromatic to be” carbon has rarely been addressed. It has been found that 4-trifluoromethyl-p-quinol silyl ethers, the readily available and relatively stable compounds, can act as dielectrophiles to be applied to multi-component reactions for the synthesis of various trifluoromethylated arenes. Catalyzed by In(OTf)3, 4-trifluoromethyl-p-quinol silyl ethers react with C-, N-, and S-nucleophiles, respectively, in a regiospecific 1,2-addition manner to generate the corresponding highly reactive electrophilic intermediates. Further reaction of the in-situ generated electrophiles with a C-nucleophile followed by spontaneous aromatization enables the construction of functionalized trifluoromethyl arenes. This three-component, double nucleophilic addition/aromatization reaction based on the pre-introduction of a trifluoromethyl group onto an “aromatic to be” carbon provides a divergent strategy for the synthesis of trifluoromethylated arenes under mild reaction conditions in a single operation.

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Sulfur(IV)-Mediated Transformations: From Ylide Transfer to Metal-Free Arylation of Carbonyl Compounds

Cited by 145 publications

References 106 publications

Regioselective synthesis of C3 alkylated and arylated benzothiophenes

Regioselective synthesis of C3 alkylated and arylated benzothiophenes

Synthetic journey towards transition metal-free arylations

4-Trifluoromethyl-p-quinols as dielectrophiles: three-component, double nucleophilic addition/aromatization reactions

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