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Relevant academic research and scientific papers

Ni(II) Precatalysts Enable Thioetherification of (Hetero)Aryl Halides and Tosylates and Tandem C?S/C?N Couplings

Ni-catalyzed C?S cross-coupling reactions have received less attention compared with other C-heteroatom couplings. Most reported examples comprise the thioetherification of most reactive aryl iodides with aromatic thiols. The use of C?O electrophiles in this context is almost uncharted. Here, we describe that preformed Ni(II) precatalysts of the type NiCl(allyl)(PMe2Ar’) (Ar’=terphenyl group) efficiently couple a wide range of (hetero)aryl halides, including challenging aryl chlorides, with a variety of aromatic and aliphatic thiols. Aryl and alkenyl tosylates are also well tolerated, demonstrating, for the first time, to be competent electrophilic partners in Ni-catalyzed C?S bond formation. The chemoselective functionalization of the C?I bond in the presence of a C?Cl bond allows for designing site-selective tandem C?S/C?N couplings. The formation of the two C-heteroatom bonds takes place in a single operation and represents a rare example of dual electrophile/nucleophile chemoselective process.

Copper-Catalyzed Intermolecular Functionalization of Unactivated C(sp3)-H Bonds and Aliphatic Carboxylic Acids

Intermolecular functionalization of C(sp3)-H bonds and aliphatic carboxylic acids enables the efficient synthesis of high value-added organic compounds from readily available starting materials. Although methods involving hydrogen atom transfer have been developed for such functionalization, these methods either work for only activated C(sp3)-H bonds or bring in a narrow set of functional groups. Here we describe a Cu-catalyzed process for the diverse functionalization of both unactivated C(sp3)-H bonds and aliphatic carboxylic acids. The process is enabled by the trapping of alkyl radicals generated through hydrogen atom abstraction by arylsulfonyl-based SOMO-philes, which introduces a large array of C, N, S, Se, and halide-based functional groups. The chemoselectivity can be switched from C-H functionalization to decarboxylative functionalization by matching the bond dissociation energy of the hydrogen atom transfer reagent with that of the target C-H or O-H bond.

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

A nickel-catalyzed aryl thioether metathesis has been developed to access high-value thioethers. 1,2-Bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional-group-tolerant reaction. Furthermore, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis that does not involve alkene bonds. In-depth organometallic studies support a reversible Ni0/NiII pathway to product formation. Overall, this work not only provides a more sustainable alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information that are highly relevant to the further development and application of unusual single-bond metathesis reactions.

Palladium-catalyzed thiolation of alkanes and ethers with arylsulfonyl hydrazides

A new method for the preparation of alkyl aryl sulfides through direct oxidative thiolation of alkanes or ethers with arylsulfonyl hydrazides using di-tert-butyl peroxide (DTBP) as an oxidant catalyzed by Pd(OAc)2 has been reported. The C-H bonds in various alkanes or ethers were successfully converted into C-S bonds to yield the corresponding sulfides in moderate to good yields. the Partner Organisations 2014.

A well-defined (POCOP)Rh catalyst for the coupling of aryl halides with thiols

This article describes a well-defined pincer-Rh catalyst for C-S cross-coupling reactions. (POCOP)Rh(H)(Cl) serves as an active precatalyst for the coupling of aryl chlorides and bromides with aryl and alkyl thiols under reasonable conditions (3% mol cat., 110 °C, 2-24 h, >90% yield). For select substrates, >90% yields were obtained with catalyst loading as low as 0.1%. Key mechanistic intermediates have been isolated and fully characterized, including (POCOP)Rh(Ph)(SPh) (6a) and (POCOP)Rh(SPh2) (6b). The aryl/bis(phosphinite) (POCOP)Rh system has been shown to favor aryl thiolate reductive elimination at elevated temperatures and in some cases at room temperature, compared with the analogous diarylamido/bis(phosphine) (PNP)Rh pincer system. Concerted reductive elimination has been studied with 6a directly and in the presence of aryl bromide and aryl chloride traps. This investigation demonstrates a clear rate dependence on aryl chloride concentration during catalysis, a dependence that is absent when using aryl bromides. The rate of catalysis is dramatically reduced or brought to zero for ortho-tolyl halides, which can be traced to slower C-S coupling and slower carbon-halogen oxidative addition for ortho-substituted aryls. The influence of the sterics in the thiol component is less straightforward. The S-H oxidative addition product (POCOP)Rh(H)(SPh) (16) has been fully characterized and its reactivity has been examined, resulting in the isolation of the sodium-thiolate adduct (POCOP)Rh(NaSPh) (19). The solid-state structure of 19 shows Na interactions not only with sulfur, but also with a neighboring Rh and the chelating aryl carbon of the pincer framework. The reactivity of 16 and 19 indicates that these potential side products should not hinder catalysis.

Efficient recyclable CuI-nanoparticle-catalyzed S-arylation of thiols with aryl halides on water under mild conditions

CuI nanoparticles efficiently catalyzed the C-S cross coupling of aryl and alkyl thiols with aryl halides in the absence of ligands on water under mild conditions. A wide range of diaryl sulfides and aryl alkyl sulfides are synthesized in good to excellent yields utilizing this protocol. This procedure is particularly noteworthy given its mild conditions, avoiding the undesired formation of disulfides through oxidation of thiols. The recovery and successful reutilization of the catalyst is described. Furthermore, the directed synthesis of bisarylated product is presented. The Royal Society of Chemistry 2012.

Carbon-sulfur bond formation of challenging substrates at low temperature by using Pd-PEPPSI-IPent

Aryl thiols made cool and quick: The coupling of alkyl, aryl, and silyl thiols to hindered, deactivated aryl bromides and chlorides has been achieved under the most mild temperatures yet reported (i.e., room temperature to 40°C). The bulk afforded by the di-2,6-(3-propylphenyl)imidazolium-derived Pd-PEPPSI-IPent catalyst is believed to actively promote the critical reductive elimination step of the catalytic cycle, thereby eliminating the formation of poisonous off-cycle dimeric resting states that have plagued Pd-catalyzed sulfination reactions.

Facile preparation of aryl sulfides using palladium catalysis under mild conditions

A convenient method for C-S cross-coupling of aryl bromides with various thiols has been developed that involves the use of a 1,1′- bis(diphenylphosphino)ferrocene (DPPF)-ligated palladium complex with N,N-diisopropylethylamine (DIPEA) as the base. This coupling is tolerant of a wide range of functional groups, including hydroxy, amino, cyano, nitro, formyl, and carboxyl groups. Georg Thieme Verlag Stuttgart - New York.

CATALYSTS FOR ARYL SULFIDE SYNTHESIS AND METHOD OF PRODUCING ARYL SULFIDES

The present invention relates to the formation of aryl sulfides and aryl thiols from aryl halides and thiols, thiolates or thiolate equivalents. The present invention provides a catalyst for the coupling of aryl halides with alkyl or aryl thiols or a hydrogen sulfide equivalent to form aryl alkyl, aryl silyl or diaryl sulfides. The reaction encompasses bromoarenes and other similar compounds containing leaving groups as well as nitrile, ester, keto, free hydroxyl, free amino, free carboxylic acid and other common functionalities. The invention can be used to prepare pharmaceutical compounds, especially including their intermediates, agricultural agents and aryl sulfide polymers.

Highly efficient and functional-group-tolerant catalysts for the palladium-catalyzed coupling of aryl chlorides with thiols

The cross-coupling reaction of aryl chlorides with aliphatic and aromatic thiols catalyzed by palladium complexes of the strongly binding bisphosphine CyPF-tBu ligand (1) is reported. Most of the reactions catalyzed by complexes of ligand 1 occur with turnover numbers that exceed those of previous catalysts by two orders of magnitude. The reactions occur with excellent yields, broad scope and high tolerance of functional groups. Coupling of aryl halides with thiols in the presence of low loadings of catalysts derived from other Josiphos type ligands, as well as ligands of other structural types, are also described.