Cs<sub>2</sub>CO<sub>3</sub>-promoted cross-dehydrogenative coupling of thiophenols with active methylene compounds

Chen, Qian; Wen, Chunxiao; Huang, Yangen; Yan, Xinxing; Zeng, Jiekun

doi:10.1039/c7ra06904a

Cited by 33 publications

(18 citation statements)

References 76 publications

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“…Later, other methodologies based on the oxidative coupling of thiols and underivatized carbonyl compounds have appeared in the literature [20a,b,e,f,h–o,t] . For example, 1,3‐diketones have been further studied in the following reports.…”

Section: Methods For the Synthesis Of α‐Sulfenylated Carbonyl Compoundsmentioning

confidence: 99%

“…In this respect, the Cs 2 CO 3 ‐promoted CDC coupling of thiols with β‐diketones under aerobic conditions has recently been reported (Scheme 11). [20l] The reaction is performed in air and therefore, the use of stronger oxidants is avoided. Halogen‐based reagents are not required and only 1 equivalent of a non‐toxic inorganic base (Cs 2 CO 3 ) is used.…”

Section: Methods For the Synthesis Of α‐Sulfenylated Carbonyl Compoundsmentioning

confidence: 99%

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Assessing Methodologies to Synthesize α‐Sulfenylated Carbonyl Compounds by Green Chemistry Metrics

Margalef

Samec

2020

ChemSusChem

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α‐Sulfenylated carbonyl compounds are important both as active pharmaceutical ingredients and as intermediates in organic synthesis. Owing to their relevance in synthetic organic chemistry, this Minireview focuses on assessing the most relevant synthetic procedures based on green chemistry metrics. The Minireview starts with the traditional routes and then focuses on more recently developed methodologies. These routes include sulfenylating reagents using organocatalysis, cross‐dehydrogenative couplings using in situ halogenations to prevent reactive intermediates in high concentrations, oxidative couplings using terminal oxidants such as DDQ or TEMPO, and redox‐neutral couplings using transition metal catalysis. These methodologies have been evaluated on the basis of atom economy, E factor, and the safety and toxicity of the transformations and the solvents used. Besides using green metrics to evaluate these novel methodologies, the synthetic utility is also assessed with regard to the availability of starting materials and the generality of the reactions. This Minireview aims to inspire researchers to apply green assessments to other methodologies and also for them to take measures to increase the greenness of their developed transformations.

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Section: Methods For the Synthesis Of α‐Sulfenylated Carbonyl Compoundsmentioning

confidence: 99%

Section: Methods For the Synthesis Of α‐Sulfenylated Carbonyl Compoundsmentioning

confidence: 99%

Assessing Methodologies to Synthesize α‐Sulfenylated Carbonyl Compounds by Green Chemistry Metrics

Margalef

Samec

2020

ChemSusChem

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“…In an attempt to develop a new metal‐free C−S coupling methodogloy for active methylene compounds, Chen et al [98] . utilised the oxidative approach of CDC using air as an oxidant under mild condition.…”

Section: Sulfenylationmentioning

confidence: 99%

Transition Metal‐Free Sulfenylation of C−H Bonds for C−S Bond Formation in Recent Years: Mechanistic Approach and Promising Future

et al. 2021

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Transition metal‐free sulfenylation of C−H bonds for C−S bond formation has recently emerged as sustainable protocols for the functionalisation of various molecules. Researchers have extensively developed such protocols for the construction of biologically relevant sulfur scaffolds. There has been a gradual shift from metal‐catalyzed to metal‐free C−S bond formation methodologies, because the latter offer environmentally benign and inherently safe access to novel synthetic routes in organic chemistry. The present review offers a dynamic discussion on recent advances in transition metal‐free C−S bond formation via C−H bond functionalization using different surrogate sulfenylating reagents. The review has comprehensively been devoted to radical and ionic mechanistic approaches. Some simple and eco‐friendly reagents for sulfenylation viz. tertbutyl hydrogen peroxide (TBHP), hydrogen peroxide (H2O2), iodine/potassium persulphate (I2/K2S2O8), inorganic bases, strong organic acids, iodine, I2/triphenyl phosphine (PPh3), N‐chlorosuccinamide (NCS), N‐bromosuccinamide (NBS), potassium iodate (KIO3), I2/bovine serum albumin (BSA), tetrabutyl ammonium iodide (TBAI)/HBr and graphene oxide along with their mechanistic approach has been detailed in this review. Moreover, modern methods for the C−S bond formation i. e., biocatalyst, electrochemical and visible light induced sulfenylation, and traditional sulfenylation methodologies have also been incorporated.

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“…3.4 硫自由基与 C(sp 3 )-H 键的反应 2013 年, 邓国军课题组 [34] 2017 年, 本课题组 [36] 实现了空气氛围下 1,3-二羰基化合物的 C(sp 3 )-H 键硫醚化反应(Scheme 32). 在室温下, 硫酚在碱存在下被氧气氧化为二硫化物.…”

Section: 硫氰基自由基与碳碳双键的反应unclassified

“…2018 年, 王震课题组 [39] 以 3-氧代丁酰胺或丁酸酯作为活泼亚甲基化合物, 在氧气氛围下与硫酚(醇)作用实现了硫醚化/C-C 键裂解反应, 以高产率得到 α-硫取代的酰胺/酯(Scheme 33). 该反应中的硫醚化过程与本课题组 [36] 报道的反应机理类似, C-C 键裂解过程为硫醚化产物在碱作用下发生了脱羧. 随后, 该课题组 [40] 发现 3-氧代丁酰胺在氧气氛围下与硫酚发生 α-双硫醚化/C-C 键裂解反应, 以高产率得到二硫缩醛类化合物(Scheme 34).…”

Section: 硫氰基自由基与碳碳双键的反应unclassified

Recent Progress in the Construction of S—S, P—S and C—S Bonds Involving O₂-Initiated Sulfur-Centered Radicals

Xi¹,

Ou²,

Liu³

et al. 2021

Chinese Journal of Organic Chemistry

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Sulfur-containing organic compounds have been widely used in organic synthesis, pharmaceuticals, pesticides and functional materials. Thus, the development of green, mild and highly efficient methodologies for the synthesis of organosulfur compounds is of great importance. Some sulfur-containing compounds can be directly initiated by O2 as the ideal green oxidant to generate sulfur-centered radicals, and the corresponding radical reactions provide a novel approach to the construction of S-S, P-S and C-S bonds. These reactions can be performed under mild conditions without the use of toxic reagents, transition metals and strong oxidants. In this review, the recent progress in the construction of S-S, P-S and C-S bonds involving O2-initiated sulfur-centered radicals is introduced on the basis of different reaction types.

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Cs₂CO₃-promoted cross-dehydrogenative coupling of thiophenols with active methylene compounds

Abstract: α-Sulfenylation of carbonyl compounds has been achieved via Cs2CO3-promoted aerobic cross-dehydrogenative coupling of thiophenols with active methylene compounds.

Cited by 33 publications

References 76 publications

Assessing Methodologies to Synthesize α‐Sulfenylated Carbonyl Compounds by Green Chemistry Metrics

Assessing Methodologies to Synthesize α‐Sulfenylated Carbonyl Compounds by Green Chemistry Metrics

Transition Metal‐Free Sulfenylation of C−H Bonds for C−S Bond Formation in Recent Years: Mechanistic Approach and Promising Future

Recent Progress in the Construction of S—S, P—S and C—S Bonds Involving O₂-Initiated Sulfur-Centered Radicals

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Cs2CO3-promoted cross-dehydrogenative coupling of thiophenols with active methylene compounds

Abstract: α-Sulfenylation of carbonyl compounds has been achieved via Cs2CO3-promoted aerobic cross-dehydrogenative coupling of thiophenols with active methylene compounds.

Cited by 33 publications

References 76 publications

Assessing Methodologies to Synthesize α‐Sulfenylated Carbonyl Compounds by Green Chemistry Metrics

Assessing Methodologies to Synthesize α‐Sulfenylated Carbonyl Compounds by Green Chemistry Metrics

Transition Metal‐Free Sulfenylation of C−H Bonds for C−S Bond Formation in Recent Years: Mechanistic Approach and Promising Future

Recent Progress in the Construction of S—S, P—S and C—S Bonds Involving O2-Initiated Sulfur-Centered Radicals

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Product

Resources

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Cs₂CO₃-promoted cross-dehydrogenative coupling of thiophenols with active methylene compounds

Recent Progress in the Construction of S—S, P—S and C—S Bonds Involving O₂-Initiated Sulfur-Centered Radicals