Cobalt‐Catalyzed Reduction of Aryl Sulfones to Arenes by Means of Alkylmagnesium Reagents

Fukuda, Jun Ichi; Nogi, Keisuke; Yorimitsu, Hideki

doi:10.1002/ajoc.201800473

Cited by 14 publications

(7 citation statements)

References 48 publications

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“…Para ‐cyanobenzene sulfonyl fluoride reacted sluggishly under either aforementioned conditions, but gave 68–72 % yield when Co(acac) 3 was used as an additive instead of Cu(IPr)Cl ( 28 ). Cobalt complexes have previously been implicated in the reduction of sulfones via C‐S oxidative addition, which might explain the benefit of this cobalt additive [36] . Supporting this hypothesis, Co(acac) 3 furnished a small amount of cross coupling product even in the absence of the Pd catalyst in the case of PyFluor (Table S1).…”

Section: Methodsmentioning

confidence: 69%

“…Cobalt complexes have previously been implicated in the reduction of sulfones via C-S oxidative addition, which might explain the benefit of this cobalt additive. [36] Supporting this hypothesis, Co(acac) 3 furnished a small amount of cross coupling product even in the absence of the Pd catalyst in the case of PyFluor (Table S1). Nevertheless, most substrates benefitted more from the addition of Cu(IPr)Cl than from Co(acac) 3 .…”

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confidence: 77%

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Desulfonative Suzuki–Miyaura Coupling of Sulfonyl Fluorides

Chatelain

Muller

et al. 2021

Angew Chem Int Ed

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Sulfonyl fluorides have emerged as powerful "click" electrophiles to access sulfonylated derivatives. Yet, they are relatively inert towards C À C bond forming transformations, notably under transition-metal catalysis. Here, we describe conditions under which aryl sulfonyl fluorides act as electrophiles for the Pd-catalyzed Suzuki-Miyaura cross-coupling. This desulfonative cross-coupling occurs selectively in the absence of base and, unusually, even in the presence of strong acids. Divergent one-step syntheses of two analogues of bioactive compounds showcase the expanded reactivity of sulfonyl fluorides to encompass both SÀNu and CÀC bond formation. Mechanistic experiments and DFT calculations suggest oxidative addition occurs at the CÀS bond followed by desulfonation to form a Pd-F intermediate that facilitates transmetalation.

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Section: Methodsmentioning

confidence: 69%

mentioning

confidence: 77%

Desulfonative Suzuki–Miyaura Coupling of Sulfonyl Fluorides

Chatelain

Muller

et al. 2021

Angew Chem Int Ed

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“…Thus, the reaction of alkyl Grignard reagents with electrophilic species can be utilized to perform reduction of the organic molecules. Several examples of transition-metal-catalyzed reduction reactions using alkyl Grignard reagents have been reported . We describe herein ligand-controlled nickel-catalyzed selective alkylation and reduction of allylic alcohols with alkyl Grignard reagents.…”

Section: Introductionmentioning

confidence: 99%

Nickel-Catalyzed Alkylation or Reduction of Allylic Alcohols with Alkyl Grignard Reagents

Yang

Wang

2020

J. Org. Chem.

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By choosing different phosphine ligands, nickel-catalyzed selective alkylation and reduction of allylic alcohols with alkyl Grignard reagents were performed. The reaction using Ni(dppe)Cl2 as the catalyst resulted in the cross-coupling of allylic alcohols with primary alkyl Grignard reagents and cyclopropylmagnesium bromide. The reaction catalyzed by the combination of Ni(PCy3)2Cl2 and dcype led to the reduction of allylic alcohols. Secondary alkyl Grignard reagents except cyclopropylmagnesium bromide always led to reduction of allylic alcohols using either Ni(dppe)Cl2 or Ni(PCy3)2Cl2/dcype as the catalyst. In the reductive reaction β-H-containing alkyl Grignard reagents were required.

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“…However, typical nucleophiles for Tsuji–Trost-type reactions are either heteroatoms or stabilized carbanions, e.g., enolates, deprotonated sulfones and alkynes. , In contrast, the use of organomagnesium compounds is plagued by β-hydride elimination of the organometallic reagent or umpolung of the π-allyl palladium complex into a nucleophile. When we examined the palladium-catalyzed allylic substitution with diethylzinc, we observed deoxygenation, presumably via β-hydride elimination and subsequent reductive elimination . Although there have been reports by Maulide and co-workers to suppress those competing pathways and promote reductive elimination, their studies were limited to diethylzinc and required non-commercially available ligands .…”

mentioning

confidence: 99%