Disulfide‐Directed C–H Hydroxylation for Synthesis of Sulfonyl Diphenyl Sulfides and 2‐(Phenylthio)phenols with Oxygen as Oxidant

Wang, Long; Xie, Yi‐Bi; Huang, Nianyu; Zhang, Nuonuo; Li, Dejiang; Hu, Yinchang; Liu, Mingguo; Li, Dongsheng

doi:10.1002/adsc.201600861

Cited by 53 publications

(13 citation statements)

References 49 publications

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“…) . Later, Wang and co‐workers introduced a direct disulfide‐directed C─H activation for the synthesis of thiophenols from disulfide and arylboronic acid with oxygen as the oxidant . However, none of the previous methods for 2‐(phenylthio)phenol derivatives synthesis could achieve recycling of the catalyst .…”

Section: Introductionmentioning

confidence: 99%

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

Zhang

Wang

et al. 2020

J of Chemical Tech & Biotech

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BACKGROUND Aromatic thioether derivatives exist widely in natural products and have significant applications in modern synthesis and the pharmaceutical industry; for example, 2‐sulfanylphenols and arylthioquinones are important intermediates in the processing of anticancer, antibiotic, antivirus and antimalarial drugs. Direct C─H hydroxylation was considered as one of the efficient methods for the synthesis of these compounds. Homogeneous transition metal catalysts usually were used through a cross‐coupling of halogen‐substituted phenols with thiophenols. However, from the perspectives of sustainable development and easy recovery, it is necessary to develop an efficient and recoverable catalytic system to realize the synthesis of aromatic thioether derivatives with good efficiency and recyclability. RESULTS The heterogeneous catalyst [Cu(binap)I]2@HT in the present work showed good catalytic activity for the C─H hydroxylation of benzenethiol and phenylboronic acid. The catalytic system was tolerant to various substituents including alkyl, alkoxy, ester, halogen or trifluoromethyl on the phenyl ring of the thiophenols or arylboric acids. In addition to electron‐donating groups, the products with strong electron‐withdrawing groups, such as methyl formylate and trifluoromethyl also were achieved with good yields at 90 °C for 12 h (68% and 66%, respectively). Repeated experiment results showed that the catalyst could be reused at least five times without obvious decrease in catalytic activity. CONCLUSION A BINAP‐Cu complex supported on hydrotalcite was prepared and used as a heterogeneous catalyst for the C─H activation of thiophenol under mild reaction conditions. Through a cascade C─H hydroxylation and further oxidation process, 2‐Sulfanylphenols and arylthioquinones could be obtained with moderate‐to‐good yields for a series of 2‐(phenylthio)phenol derivatives using the heterogeneous catalyst [Cu(binap)I]2@HT. In addition, this heterogeneous catalyst showed good recylbility. © 2020 Society of Chemical Industry

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Section: Introductionmentioning

confidence: 99%

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

Zhang

Wang

et al. 2020

J of Chemical Tech & Biotech

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“…Based on our previous research, [26][27][28][29][30][31][32] herein, we report a method to efficiently synthesize diaryl sulfide compounds by utilizing copper-doped manganese oxide octahedral molecular sieves (Cu-OMS-2) to catalyze the heterogeneous C-S coupling reaction of thiophenols and aryl halides (Scheme 1(c)).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of diaryl sulfides based on copper-doped OMS-2

Liu

et al. 2020

Journal of Chemical Research

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We describe a practical protocol for efficiently preparing diaryl sulfide compounds using Cu–OMS-2 as the catalyst. Cu–OMS-2 originates from manganese oxide octahedral molecular sieves modified with copper ions and catalyzes the C–S coupling reaction of substituted thiophenols and aryl halides. This protocol has the advantages of environmental friendliness, simple operation, high yields, good tolerance of functional groups, and the Cu–OMS-2 catalytic material can be recycled several times.

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“…reported the synthesis of 2‐(phenylthio)phenols via copper‐catalyzed hydroxylation and S‐arylation and some other works . We have also described a disulfide‐directed C−H hydroxylation . Several other scientists are also working on C−H activation through the sulfur‐directed group .…”

Section: Introductionmentioning

confidence: 99%

“…In addition, in order to make further understanding of this tandem reaction, we proposed a possible reaction mechanism through according to the references and our previous studies (Scheme ) . First, in the presence of DMSO, the key intermediate 6 was formed; then intermediate 6 reacted with aryl iodide 2 to produce intermediate 7 ; and then the disulfides 1 captured intermediate 7 to generate the key intermediate 8 ; and then selective hydroxylation of the aromatic ring was occured in the intermediate 8 to produced intermediate 9 .…”

Section: Introductionmentioning

confidence: 99%

Efficient Synthesis of Sulfonyl Diphenylsulfides Catalyzed via Cu–MOF of PCN‐6’

et al. 2019

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Disulfide‐Directed C–H Hydroxylation for Synthesis of Sulfonyl Diphenyl Sulfides and 2‐(Phenylthio)phenols with Oxygen as Oxidant

Abstract: Scheme 6. Selectivity experiments of an unsymmetrical disulfide with iodobenzene. Scheme7.Hammettplot of various aryl iodides.

Cited by 53 publications

References 49 publications

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

Synthesis of diaryl sulfides based on copper-doped OMS-2

Efficient Synthesis of Sulfonyl Diphenylsulfides Catalyzed via Cu–MOF of PCN‐6’

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