O-(Mesitylsulfonyl)hydroxylamine

Boche, Gernot; Mendiola, Javier; Rincón, Juan A.; Mateos, Carlos; Soriano, José; Frutos, Óscar de

doi:10.1002/047084289x.rm055m.pub2

Cited by 2 publications

(2 citation statements)

References 72 publications

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“…With these optimal conditions in hand, we had to find the most suitable aminating agent in order to elaborate a fully compatible protocol to convert pyridines into 1,2-diazepines in a single-flask operation (Figure bottom, inset table). After querying the literature (see details in the Supporting Information), we selected MSH ( O -(mesitylsulfonyl)hydroxylamine) for several reasons: (a) it can be easily prepared in 2 steps from cheap and commercially available reactants and collected by filtration; (b) as an hydrate, usually between 20 and 40% water, it is an air and moisture tolerant solid, which could be stored under regular atmosphere for several days without any noticeable alteration (see the Supporting Information for potential hazard) . Thus, we could generate the 1-aminopyridinium in situ from the parent pyridine 23 within 1 h at 40 °C.…”

Section: Results and Discussionmentioning

confidence: 99%

“…After querying the literature (see details in the Supporting Information), we selected MSH (O-(mesitylsulfonyl)hydroxylamine) for several reasons: (a) it can be easily prepared in 2 steps from cheap and commercially available reactants and collected by filtration; (b) as an hydrate, usually between 20 and 40% water, it is an air and moisture tolerant solid, which could be stored under regular atmosphere for several days without any noticeable alteration (see the Supporting Information for potential hazard). 47 Thus, we could generate the 1-aminopyridinium in situ from the parent pyridine 23 within 1 h at 40 °C. Noteworthy, 4 Å molecular sieves appeared to increase the yield, although it is not mandatory to achieve synthetically useful yields.…”

Section: Journal Of the American Chemicalmentioning

confidence: 99%

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Dearomatization of Pyridines: Photochemical Skeletal Enlargement for the Synthesis of 1,2-Diazepines

Boudry,

Bourdreux,

Marrot

et al. 2024

J. Am. Chem. Soc.

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In this report, we developed a unified and standardized one-pot sequence that converts pyridine derivatives into 1,2-diazepines by inserting a nitrogen atom. This skeletal transformation capitalizes on the in situ generation of 1-aminopyridinium ylides, which rearrange under UV light irradiation. A thorough evaluation of the key parameters (wavelength, reaction conditions, activating agent) allowed us to elaborate on a simple, mild, and user-friendly protocol. The model reaction was extrapolated to more than 40 examples, including drug derivatives, affording unique 7-membered structures. Mechanistic evidence supports the transient presence of a diazanorcaradiene species. Finally, pertinent transformations of the products, including ring contraction reactions to form pyrazoles, were conducted and paved the way to a broad application of the developed protocol.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Journal Of the American Chemicalmentioning

confidence: 99%

Dearomatization of Pyridines: Photochemical Skeletal Enlargement for the Synthesis of 1,2-Diazepines

Boudry,

Bourdreux,

Marrot

et al. 2024

J. Am. Chem. Soc.

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Synthesis of N-Aminated Salts of Aliphatic tert-Amines, (Trialkyl)amidines, and (Pentaalkyl)guanidines by Electrophilic Amination in an Ethereal Solvent

Fujita

Arai

Kunishima

2022

CHEMICAL & PHARMACEUTICAL BULLETIN

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The electrophilic amination of nitrogen-based nucleophiles, including strong organic bases, was conducted in an Et 2 O solvent using O-(mesitylenesulfonyl)hydroxylamine. Aliphatic tert-amines and N,N,N′-(trialkyl) amidines rapidly formed precipitates of the corresponding aminated salts in high yields. The amination of the highly basic and sterically hindered N,N,N′,N′,N″-(pentaalkyl)guanidines was achieved under modified conditions, although the yields were moderate because of a competing side reaction caused by the acid-base equilibrium.

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O-(Mesitylsulfonyl)hydroxylamine

Cited by 2 publications

References 72 publications

Dearomatization of Pyridines: Photochemical Skeletal Enlargement for the Synthesis of 1,2-Diazepines

Dearomatization of Pyridines: Photochemical Skeletal Enlargement for the Synthesis of 1,2-Diazepines

Synthesis of <i>N</i>-Aminated Salts of Aliphatic <i>tert</i>-Amines, (Trialkyl)amidines, and (Pentaalkyl)guanidines by Electrophilic Amination in an Ethereal Solvent

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