Nickel‐Catalyzed Inter‐ and Intramolecular Aryl Thioether Metathesis by Reversible Arylation

Delcaillau, Tristan; Bismuto, Alessandro; Lian, Zhong; Morandi, Bill

doi:10.1002/anie.201910436

Cited by 73 publications

(49 citation statements)

References 60 publications

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“…mp 55.4-57.1°C. [24] The title compound was isolated by column chromatography (petroleum ether) as a colorless oil (75 mg, 62 % yield). (4-Methoxyphenyl)(phenyl)sulfane (4 a) [25] The title compound was isolated by column chromatography (petroleum ether) as a colorless oil (89 mg, 82 % yield).…”

Section: 2-bis(4-(tert-butyl)phenyl)disulfane (2 F)mentioning

confidence: 99%

Forging C−S(Se) Bonds by Nickel‐catalyzed Decarbonylation of Carboxylic Acid and Cleavage of Aryl Dichalcogenides

Zhou

Zhu

2021

Eur J Org Chem

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A nickel‐catalyzed decarbonylation of carboxylic acids cross‐coupling protocol has been developed for the straightforward C−S(Se) bond formation. This reaction is promoted by a commercially‐available, user‐friendly, inexpensive, air and moisture‐stable nickel precatalyst. Various carboxylic acids and a wide range of aryl dichalcogenide substrates were tolerated in this process which afforded products in good to excellent yields. In addition, the present reaction can be conducted on gram scale in good yield.

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Section: 2-bis(4-(tert-butyl)phenyl)disulfane (2 F)mentioning

confidence: 99%

Forging C−S(Se) Bonds by Nickel‐catalyzed Decarbonylation of Carboxylic Acid and Cleavage of Aryl Dichalcogenides

Zhou

Zhu

2021

Eur J Org Chem

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“…[10][11][12][13][14] Dynamic covalent chemistry (DCC) 15 is a key feature in the synthesis of these systems; the reversibility of the reactions used for their syntheses provides self-correcting behaviour which, in turn, allows the formation of high-quality, low-defect In 2017, our group reported the Pd-catalysed C-S/C-S single-bond metathesis reaction 22 and, more recently, a Ni-catalysed version. 23 These reactions allow the facile synthesis of a number of thioether molecules and macrocycles from the corresponding thiols as nucleophiles and aryl-SR (R = H, Me) compounds as electrophiles by driving the equilibrium towards product formation (excess of nucleophile and precipitation of LiSMe or Li2S salts). Interestingly, depolymerisation of PPS was achieved in 85% yield, showing the potential of the reaction for materials science.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Versatile, Porous Poly-Arylthioethers by Reversible Pd-Catalysed C–S/C–S Metathesis

Rivero‐Crespo¹,

Toupalas²,

Morandi³

2021

Preprint

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Porous organic frameworks have shown a number of promising properties; however, their industrial application is usually hampered due to the lability of their linkages (imine, boroxine, etc.). Inspired by the outstanding chemical, mechanical and thermal resistance of the 1D polymer polyphenylene sulfide (PPS), we hypothesized that 2D and 3D poly-arylthioether frameworks would merge the attractive features common to porous frameworks and PPS in a single material. Herein, we report a Pd-catalysed C–S/C–S metathesis-based method to prepare new porous poly-arylthioether frameworks in good yields. The self-correcting nature of the process has enabled the synthesis of new, robust materials with high surface areas. Despite the frameworks’ extreme resistance to harsh chemicals, they can be fully recycled to recover the original building blocks using the same catalytic reaction. In addition, we demonstrate preliminary results showing that these materials have great potential in several environmentally relevant applications including metal capture, metal sensing and heterogeneous catalysis. In a broader context, these results clearly demonstrate the untapped potential of emerging single-bond metathesis reactions in the preparation of new materials.

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“…imine, boronate Our group has previously developed transition-metal-catalysed C-S/C-S single-bond metathesis reactions and showcased their utility in small molecule synthesis. 23,24 These reactions allow the facile synthesis of a number of thioether molecules and macrocycles from the corresponding thiols as nucleophiles and aryl-SR (R = H, Me) compounds as electrophiles by driving the equilibrium towards product formation (excess of nucleophile and precipitation of LiSMe or Li2S salts). Interestingly, depolymerisation of PPS was achieved in 85% yield, showing the potential of the reaction for polymer recycling.…”

Section: Introductionmentioning

confidence: 99%

Preparation of Recyclable and Versatile Porous Poly-Arylthioethers by Reversible Pd-Catalysed C–S/C–S Metathesis

Rivero‐Crespo

Toupalas

Morandi

2021

Preprint

Self Cite

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Porous organic polymers have shown a number of promising properties; however, their application is usually hampered due to the lability of their linkages. Inspired by the outstanding chemical, mechanical and thermal resistance of the 1D polymer polyphenylene sulphide (PPS), we have designed a new family of 2D and 3D poly-arylthioethers, synthesised via a mild Pd-catalysed C-S/C-S metathesis-based method, that merges the attractive features common to porous polymers and PPS in a single material. In addition, the method is highly modular, allowing to easily introduce application-oriented functionalities in the materials for a series of environmentally relevant applications including metal capture, metal sensing and heterogeneous catalysis. Moreover, despite their extreme chemical resistance, the polymers can be easily recycled to recover the original monomers, offering an attractive perspective for their sustainable use. In a broader context, these results clearly demonstrate the untapped potential of emerging single-bond metathesis reactions in the preparation of new, recyclable materials ester, boroxine) used to construct these materials under self-correcting conditions makes them unstable towards moderately harsh media (e.g. water, pH, temperature, pressure), often hampering their industrial application. For this reason, the synthesis of analogous yet more stable materials containing stronger covalent bonds in a DCClike manner is highly attractive. Ideally, such new materials should, despite their high chemical strength, be recyclable to their monomers to allow for their circular use in accordance with sustainable chemistry goals. 16 Sulphur containing 1D-polymers like polyphenylene sulphide (PPS) have seen widespread use in industry as insulators and replacements for metal parts due to their extremely high chemical, thermal and mechanical resistance, as illustrated by the large number of patents (>100'000) in this area. 17,18 However, the harsh conditions required for their synthesis (Scheme 1a, polycondensation > 250 °C, Na2S, autogenous pressure) 17,19 and the extreme stability of the thioether bonds, make it difficult to fine-tune PPS's properties (Mw, cross-linking, polydispersity, etc.). Moreover, this dramatically limits the possibility to access more complex poly-arylthioetherbased structures with 2D or 3D cores, despite their potential to exhibit advanced features such as porosity, metalbinding ability or optoelectronic properties, among others. The synthesis of such advanced materials, which should be analogous to PPS in terms of chemical, thermal and mechanical stability, would be a step forward towards the industrial application of porous polymers. Among the extremely scarce examples of porous polyarylthioether-based materials, 20,21 Swager and co-workers reported the synthesis of thianthrene-based 2D polymers with high surface area and interesting redox properties using dynamic SNAr reactions of thiocatechols and perfluorinated aromatic compounds (Scheme 1b). 22 While this synthetic method provide...

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Nickel‐Catalyzed Inter‐ and Intramolecular Aryl Thioether Metathesis by Reversible Arylation

Cited by 73 publications

References 60 publications

Forging C−S(Se) Bonds by Nickel‐catalyzed Decarbonylation of Carboxylic Acid and Cleavage of Aryl Dichalcogenides

Forging C−S(Se) Bonds by Nickel‐catalyzed Decarbonylation of Carboxylic Acid and Cleavage of Aryl Dichalcogenides

Preparation of Versatile, Porous Poly-Arylthioethers by Reversible Pd-Catalysed C–S/C–S Metathesis

Preparation of Recyclable and Versatile Porous Poly-Arylthioethers by Reversible Pd-Catalysed C–S/C–S Metathesis

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