Catalyst Selection Facilitates the Use of Heterocyclic Sulfinates as General Nucleophilic Coupling Partners in Palladium-Catalyzed Coupling Reactions

Markovic, Tim; Rocke, Benjamin N.; Blakemore, David C.; Mascitti, Vincent; Willis, Michael C.

doi:10.1021/acs.orglett.7b02944

Cited by 45 publications

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“…Heteroaromatic sulfones can be readily accessed from commercially available starting materials, either directly from thiols, halides or via the sulfinate salt. [ 19 , 21 ] The β‐nitrile sulfones were primarily accessed from thiols through conjugate addition into acrylonitrile and subsequent oxidation (the order of these steps could also be reversed, Scheme 1 a,b ),[ 11a , 11b ] from aryl halides using the sodium 3‐methoxy‐3‐oxopropane‐1‐sulfinate (SMOPS) reagent (Scheme 1 c ), [21] or by utilizing SO 2 surrogates, such as DABSO, to form the parent sulfinate,[ 19b , 19e , 20 ] followed by conjugate addition (Scheme 1 d ).…”

Section: Resultsmentioning

confidence: 99%

Base‐Activated Latent Heteroaromatic Sulfinates as Nucleophilic Coupling Partners in Palladium‐Catalyzed Cross‐Coupling Reactions

et al. 2021

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Heteroaromatic sulfinates are effective nucleophilic reagents in Pd0‐catalyzed cross‐coupling reactions with aryl halides. However, metal sulfinate salts can be challenging to purify, solubilize in reaction media, and are not tolerant to multi‐step transformations. Here we introduce base‐activated, latent sulfinate reagents: β‐nitrile and β‐ester sulfones. We show that under the cross‐coupling conditions, these species generate the sulfinate salt in situ, which then undergo efficient palladium‐catalyzed desulfinative cross‐coupling with (hetero)aryl bromides to deliver a broad range of biaryls. These latent sulfinate reagents have proven to be stable through multi‐step substrate elaboration, and amenable to scale‐up.

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Section: Resultsmentioning

confidence: 99%

Base‐Activated Latent Heteroaromatic Sulfinates as Nucleophilic Coupling Partners in Palladium‐Catalyzed Cross‐Coupling Reactions

et al. 2021

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“…509 Further work expanded this concept to an extensive, functional group-tolerant scope of five- and six-membered heteroaryl sulfinates. 510…”

Section: Sulfinate Salts and Derivativesmentioning

confidence: 99%

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

et al. 2019

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Organosulfur compounds have long played a vital role in organic chemistry and in the development of novel chemical structures and architectures. Prominent among these organosulfur compounds are those involving a sulfur(IV) center, which have been the subject of countless investigations over more than a hundred years. In addition to a long list of textbook sulfur-based reactions, there has been a sustained interest in the chemistry of organosulfur(IV) compounds in recent years. Of particular interest within organosulfur chemistry is the ease with which the synthetic chemist can effect a wide range of transformations through either bond formation or bond cleavage at sulfur. This review aims to cover the developments of the past decade in the chemistry of organic sulfur(IV) molecules and provide insight into both the wide range of reactions which critically rely on this versatile element and the diverse scaffolds that can thereby be synthesized.

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“…[359] Another important breakthrough in chemistry of the sulfinate building blocks was achieved by Willis and co-workers in 2017 (Scheme 39A). [360,361] They proposed carefully optimized reaction conditions for the Pd-mediated cross-couplings involving aromatic (including heterocyclic) sulfinates 35 as the nucleophilic components. Initially, the method was suggested to address the problem of 2-pyridyl-substituted substrates 35; [362] nevertheless, it could be extended to a large scope of heterocyclic substrates (Scheme 39B).…”

Section: Applications In Synthetic and Medicinal Chemistrymentioning

confidence: 99%

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

2021

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Current medicinal chemistry relies heavily on the quality of building blocks, i. e. reagents used to introduce chemical diversity into the target molecules. The last decade witnessed an emergence of many novel (or well-overlooked old) chemotypes for drug discovery, which is related to adapting new synthetic methodologies, designing new sp 3 -enriched bioisosteres, paying attention to previously underrated (or even unwanted) structural motifs, or combination thereof. In this review with 532 references, a survey of selected chemotypes that emerged recently in medicinal chemistry is provided, with a focus on the synthesis of the corresponding building blocks. Thus, saturated (hetero)aliphatic boronates, sulfonyl fluorides, sulfinates, non-classical sp 3 -enriched benzene isosteres, bicyclic morpholine/piperidine/piperazine analogs, as well as gemdifluorinated cycloalkanes (as an example of emerging fluorinated motifs) are discussed.

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Catalyst Selection Facilitates the Use of Heterocyclic Sulfinates as General Nucleophilic Coupling Partners in Palladium-Catalyzed Coupling Reactions

Cited by 45 publications

References 20 publications

Base‐Activated Latent Heteroaromatic Sulfinates as Nucleophilic Coupling Partners in Palladium‐Catalyzed Cross‐Coupling Reactions

Base‐Activated Latent Heteroaromatic Sulfinates as Nucleophilic Coupling Partners in Palladium‐Catalyzed Cross‐Coupling Reactions

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

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