Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction

Isshiki, Ryota; Kurosawa, Miki B.; Muto, Kei; Yamaguchi, Junichiro

doi:10.26434/chemrxiv.14462376.v1

Cited by 7 publications

(10 citation statements)

References 2 publications

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“…74 In 2021, Yamaguchi's group explored an aryl exchange reaction to achieve the cross-coupling of pyridyl sulfides and various aryl electrophiles (Scheme 48). 75 2-Pyridyl sulfide was employed as a sulfide donor to avoid the use of odorous and toxic thiols. This method tolerated a wide range of substrates and could effectively achieve the cleavage of C-O bonds, C-halogen bonds and C-C bonds to construct sulfides.…”

Section: C-s Bond Cleavage Of Sulfidesmentioning

confidence: 99%

Ni-catalyzed C–S bond construction and cleavage

2022

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Section: C-s Bond Cleavage Of Sulfidesmentioning

confidence: 99%

Ni-catalyzed C–S bond construction and cleavage

2022

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“…Further studies to develop other aryl exchange reactions and detailed mechanistic studies are ongoing in our laboratory. 22 ■ ASSOCIATED CONTENT * sı Supporting Information…”

Section: ■ Conclusionmentioning

confidence: 99%

Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction

et al. 2021

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A Ni-catalyzed aryl sulfide synthesis through an aryl exchange reaction between aryl sulfides and a variety of aryl electrophiles was developed. By using 2-pyridyl sulfide as a sulfide donor, this reaction achieved the synthesis of aryl sulfides without using odorous and toxic thiols. The use of a Ni/dcypt catalyst capable of cleaving and forming aryl–S bonds was important for the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, which include aromatic esters, arenol derivatives, and aryl halides. Mechanistic studies revealed that Ni/dcypt can simultaneously undergo oxidative additions of aryl sulfides and aromatic esters, followed by ligand exchange between the generated aryl–Ni–SR and aryl–Ni–OAr species to furnish aryl exchanged compounds.

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“…14,15 Yamaguchi and co-workers have reported the Ni-catalyzed transfer of an ester moiety to a range of aryl halides 16 and extended this methodology to the transfer of sulfides to different aryl electrophiles. 17 Recently, we have disclosed the Ni-catalyzed metathesis between aryl thioethers and aryl nitriles. 18 The reaction exhibited a broad substrate scope in both aryl nitriles and aryl sulfides, could be used to circumvent the need for hazardous reagents (such as cyanide salts or lowmolecular-weight thiols), and proved useful in target-oriented synthesis (Figure 1C).…”

Section: ■ Introductionmentioning

confidence: 99%

Mechanistic Investigation of the Nickel-Catalyzed Metathesis between Aryl Thioethers and Aryl Nitriles

et al. 2022

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Functional group metathesis is an emerging field in organic chemistry with promising synthetic applications. However, no complete mechanistic studies of these reactions have been reported to date, particularly regarding the nature of the key functional group transfer mechanism. Unraveling the mechanism of these transformations would not only allow for their further improvement but would also lead to the design of novel reactions. Herein, we describe our detailed mechanistic studies of the nickel-catalyzed functional group metathesis reaction between aryl methyl sulfides and aryl nitriles, combining experimental and computational results. These studies did not support a mechanism proceeding through reversible migratory insertion of the nitrile into a Ni–Ar bond and provided strong support for an alternative mechanism involving a key transmetalation step between two independently generated oxidative addition complexes. Extensive kinetic analysis, including rate law determination and Eyring analysis, indicated the oxidative addition complex of aryl nitrile as the resting state of the catalytic reaction. Depending on the concentration of aryl methyl sulfide, either the reductive elimination of aryl nitrile or the oxidative addition into the C(sp2)–S bond of aryl methyl sulfide is the turnover-limiting step of the reaction. NMR studies, including an unusual 31P–2H HMBC experiment using deuterium-labeled complexes, unambiguously demonstrated that the sulfide and cyanide groups exchange during the transmetalation step, rather than the two aryl moieties. In addition, Eyring and Hammett analyses of the transmetalation between two Ni(II) complexes revealed that this central step proceeds via an associative mechanism. Organometallic studies involving the synthesis, isolation, and characterization of all putative intermediates and possible deactivation complexes have further shed light on the reaction mechanism, including the identification of a key deactivation pathway, which has led to an improved catalytic protocol.

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Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction

Cited by 7 publications

References 2 publications

Ni-catalyzed C–S bond construction and cleavage

Ni-catalyzed C–S bond construction and cleavage

Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction

Mechanistic Investigation of the Nickel-Catalyzed Metathesis between Aryl Thioethers and Aryl Nitriles

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