Sulfur Imidations by Light‐Induced Ruthenium‐Catalyzed Nitrene Transfer Reactions

Bizet, Vincent; Bolm, Carsten

doi:10.1002/ejoc.201500220

Cited by 62 publications

(33 citation statements)

References 64 publications

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“…[66] In the presence of aRu(TPP)CO (TPP = tetraphenylporphyrin) catalyst, dioxazolones proved to be suitable substrates for nitrene transfer reactions (Scheme 21). Thea ctive catalytic species is generated by dissociation of CO from the Ru pre-catalyst, astep which can be promoted by light or thermal energy.A fter decarboxylation, the N-acyl-based Ru inter-mediate is capable of transferring the nitrene unit to thioethers and sulfoxides, [67] olefins and alkynes. [68] In the latter case,t he addition of CuCl 2 is required as ac o-catalyst allowing the formation of 2-oxazolines and oxazoles.…”

Section: Methodsmentioning

confidence: 99%

Catalytic Transformations of Functionalized Cyclic Organic Carbonates

et al. 2018

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Functionalized cyclic organic carbonates and related heterocycles have emerged as highly versatile heterocyclic substrates for ring-opening and decarboxylative catalytic transformations allowing for the development of new stereo- and enantioselective C-N, C-O, C-C, C-S and C-B bond formation reactions. Transition-metal-mediated conversions have only recently been rejuvenated as powerful approaches towards the preparation of more complex molecules. This minireview will highlight the potential of cyclic carbonates and structurally related heterocycles with a focus on their synthetic value and the mechanistic manifolds that are involved upon their conversion.

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Section: Methodsmentioning

confidence: 99%

Catalytic Transformations of Functionalized Cyclic Organic Carbonates

et al. 2018

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“…Then we speculate that the aroyl nitrene may form after the departure of benzene‐sulfonyl fluoride. Therefore, we attempted to use methyl phenyl sulfide to probe the intermediacy of the nitrene (Scheme A). But the desired product was not detected.…”

Section: Resultsmentioning

confidence: 99%

A Novel C–N Migration Rearrangement Based on N–F Compounds for the Synthesis of N‐Alkyl Diaryl Ureas

Zhao

Xie²,

Yang³

et al. 2020

Eur J Org Chem

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A novel rearrangement reaction based on the structure of N-fluoro-N-(phenylsulfonyl) benzamides (FPSBA) was developed. In the presence of base, unsymmetrical N-alkyl diaryl ureas were obtained in good yields which were accomplished through secondary alkyl phenylamines initiated 1,2-phenyl-shift migration rearrangement of N-fluoro-N-(phenylsulfonyl) benzamides. The reaction was carried out without using traditional, highly toxic reagents and noble metals. Whereas without rear- [a] Key .99. HRMS-EI (m/z) calcd. for (C 13 H 9 F 2 NO 3 S) 297.0271, found 297.0273. 2-Chloro-N-fluoro-N-(phenylsulfonyl)benzamide (1h):Following general procedure A, 1h was obtained in 89 % yield (274.2 mg, 1 mmol) as a white solid. -EI (m/z) calcd. for (C 13 H 9 FClNO 3 S) 312.9976, found 312.9978. 3-Chloro-N-fluoro-N-(phenylsulfonyl)benzamide (1i): Following general procedure A, 1i was obtained in 91 % yield (283.4 mg, 1 mmol) as a white solid. M.p.: 91.3-92.0°C. IR (KBr, cm -1 ): ν = 3089, δ = -49.54. HRMS-EI (m/z) calcd. for (C 13 H 9 FClNO 3 S) 312.9976, found 312.9973. 4-Chloro-N-fluoro-N-(phenylsulfonyl)benzamide (1j): Following general procedure A, 1j was obtained in 92 % yield (289 mg, 1 mmol) as a white solid. M.p.: 95.6-96.1°C. IR (KBr, cm -1 ): ν = 3093, δ = -49.99. HRMS-EI (m/z) calcd. for (C 13 H 9 FClNO 3 S) 312.9976, found 312.9978. 4-Bromo-N-fluoro-N-(phenylsulfonyl)benzamide (1k): Following general procedure A, 1k was obtained in 94 % yield (337 mg, 1 mmol) as a white solid. M.p.: 93.1-93.5°C. IR (KBr, cm -1 ): ν = 3100, δ = -49.97. HRMS-EI (m/z) calcd. for (C 13 H 9 FBrNO 3 S) 356.9471, found 356.9467. (1l): Following general procedure A, 1l was obtained in 98 % yield (316.2 mg, 1 mmol) as a yellow solid. M.p.: 130.5-131.2°C. IR (KBr, cm -1 ): ν = 3065, 2360, 1749, 1558, 1540, 1391, 1340. 1 H NMR (400 MHz, CDCl 3 ) δ = 8.39-8.32 (m, 2H), 8.06-8.02 (m, 2H), 7.89-7.85 (m, 2H), 7.84-7.78 (m, 1H), 7.68-7.61 (m, (C 13 H 9 N 2 O 5 S [M -F] -) 305.0232, found 305.0233. N-Fluoro-4-nitro-N-(phenylsulfonyl)benzamide Methyl 4-[Fluoro(phenylsulfonyl)carbamoyl]benzoate (1m):Following general procedure A, 1m was obtained in 99 % yield (333.7 mg, 1 mmol) as a white solid.

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“…Through one of the heteroatoms, 3‐substituted‐1,4,2‐dioxazol‐5‐one 1 interacts with the silver(I) salt to generate silver complex A [5] . The subsequent loss of CO 2 provides silver N ‐acyl nitrene complex B [29] . Then, the interaction of isocyanide 2 with N ‐acyl nitrene complex B allows an N ‐acyl nitrene transfer reaction via complex C , generating intermediate D and active silver(I) catalyst for the next cycle.…”

Section: Methodsmentioning

confidence: 99%

Silver‐Catalyzed Acyl Nitrene Transfer Reactions Involving Dioxazolones: Direct Assembly of N‐Acylureas

Yang

Xu²,

Chen

et al. 2020

Eur J Org Chem

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Dioxazolones and isocyanides are useful synthetic building blocks, and have attracted significant attention from researchers. However, the silver-catalyzed nitrene transfer reaction of dioxazolones has not been investigated to date. Herein, a silvercatalyzed acyl nitrene transfer reaction involving dioxazolones, isocyanides, and water was realized in the presence of Ag 2 O to afford a series of N-acylureas in moderate to good yields. The incorporation of an amide moiety into a molecule is of considerable importance because of the presence of this substructure in many biologically active molecules and natural products. [1] In the late 1960s, 1,4,2-dioxazol-5-ones (dioxazolones) 1 were identified by Sauer and Mayer as safe alternatives to acyl azides for N-acyl nitrene formation. [2] Owing to their low cost, ready availability, and environmental friendliness, 1,4,2dioxazol-5-ones have been extensively studied as amidating reagents in the past several years. In 2009, Dubé et al. published a pioneering method to prepare isocyanates by employing 1,4,2-dioxazol-5-ones. [3] Later, Bolm and co-workers reported the first light-induced ruthenium-catalyzed N-acyl nitrene transfer to sulfides and sulfoxides by the decarboxylation of 1,4,2dioxazol-5-ones (eq 1, Scheme 1). [4] Subsequently, dioxazolones were reported as amidating reagents for Rh-catalyzed CÀ H amidation by the Chang group. [5] Thereafter, a series of Rh-, [6] Co-, [7] and Ir-catalyzed [8] CÀ H amidation reactions were developed using this amidating reagent (eq 2, Scheme 1). Furthermore, Li, Zhu, Glorius, Ackermann, and other research groups described the cascade C À H amidation and cyclization reactions for the syntheses of various heterocycles. [9] Bruin and co-workers recently reported the fast N-acyl amidations via Cucatalyzed three-component reaction of aryl acetylenes, amines, and 1,4,2-dioxazol-5-ones (eq 3, Scheme 1). [10] However, to the best of our knowledge, the silver-catalyzed reaction of 1,4,2dioxazol-5-one via acyl nitrene has not been reported in the literature.

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Sulfur Imidations by Light‐Induced Ruthenium‐Catalyzed Nitrene Transfer Reactions

Cited by 62 publications

References 64 publications

Catalytic Transformations of Functionalized Cyclic Organic Carbonates

Catalytic Transformations of Functionalized Cyclic Organic Carbonates

A Novel C–N Migration Rearrangement Based on N–F Compounds for the Synthesis of N‐Alkyl Diaryl Ureas

Silver‐Catalyzed Acyl Nitrene Transfer Reactions Involving Dioxazolones: Direct Assembly of N‐Acylureas

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