Reaction of Oxime <i>p</i>-Toluenesulfonates and Mercaptans

Kaneda, Akira; Nagatsuka, Masaaki; Sudo, Rokuro

doi:10.1246/bcsj.40.2705

Cited by 10 publications

(2 citation statements)

References 2 publications

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“…[26] Finally, the Beckmann rearrangement can be modified in such a way that thioimidates are formed. [27,28] Scheme 1. Synthetic approaches to thioimidates.…”

Section: Introductionmentioning

confidence: 99%

Organic Synthesis with N‐Heterocyclic Carbenes of Indazole: Synthesis of Benzo(thio)imidates, Benzo[d][1,3]thiazines and Quinazoline‐4‐thiones

2015

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The N‐heterocyclic carbenes of indazole, generated by deprotonation of indazolium salts, proved to be versatile starting materials for organic synthesis. They undergo ring‐opening reactions to generate ketenimines which readily add thiols thus affording what are, to the best of our knowledge, the first examples of 2‐anilinobenzothioimidates. Water converts the ring‐opened intermediates into functionalized 2‐anilinobenzamides which can be thionated with Lawesson's reagent and subsequently cyclized with formaldehyde and propionaldehyde, respectively, to give benzo[d][1,3]thiazines and quinazoline‐4‐thiones. The outcome of the cyclization depends upon the thiobenzamide substitution pattern.

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“…[26] Finally, the Beckmann rearrangement can be modified in such a way that thioimidates are formed. [27,28] Scheme 1. Synthetic approaches to thioimidates.…”

Section: Introductionmentioning

confidence: 99%

Organic Synthesis with N‐Heterocyclic Carbenes of Indazole: Synthesis of Benzo(thio)imidates, Benzo[d][1,3]thiazines and Quinazoline‐4‐thiones

2015

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“…Treating neat cyclohexanone with hydroxylamine ⋅ HCl salt by grinding them together in a mortar, while slowly adding NaOH, yielded the corresponding pure oxime conveniently, even on large scale (120 mmol, 82 %; Scheme 1). [15] Next, under an atmosphere of nitrogen, the oxime was activated in situ as the corresponding methylsulfonate with methylsulfonyl chloride and triethylamine in MeCN at 0 °C [11c,16] . Benzotriazole was added and the mixture was heated to reflux for 2 h to facilitate the ring expansion and trap the nitrilium ion.…”

Section: Resultsmentioning

confidence: 99%

Atypical and Asymmetric 1,3‐P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes

Rong

Holtrop

Bobylev

et al. 2021

Chemistry A European J

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Novel seven‐membered cyclic imine‐based 1,3‐P,N ligands were obtained by capturing a Beckmann nitrilium ion intermediate generated in situ from cyclohexanone with benzotriazole, and then displacing it by a secondary phosphane under triflic acid promotion. These “cycloiminophosphanes” possess flexible non‐isomerizable tetrahydroazepine rings with a high basicity; this sets them apart from previously reported iminophophanes. The donor strength of the ligands was investigated by using their P‐κ1‐ and P,N‐κ2‐tungsten(0) carbonyl complexes, by determining the IR frequency of the trans‐CO ligands. Complexes with [RhCp*Cl2]2 demonstrated the hemilability of the ligands, giving a dynamic equilibrium of κ1 and κ2 species; treatment with AgOTf gives full conversion to the κ2 complex. The potential for catalysis was shown in the RuII‐catalyzed, solvent‐free hydration of benzonitrile and the RuII‐ and IrI‐catalyzed transfer hydrogenation of cyclohexanone in isopropanol. Finally, to enable access to asymmetric catalysts, chiral cycloiminophosphanes were prepared from l‐menthone, as well as their P,N‐κ2‐RhIII and a P‐κ1‐RuII complexes.

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syn‐anti Isomerizations and rearrangements

Mccarty

1970

PATAI'S Chemistry of Functional Groups

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Reaction of Oxime p-Toluenesulfonates and Mercaptans

Cited by 10 publications

References 2 publications

Organic Synthesis with N‐Heterocyclic Carbenes of Indazole: Synthesis of Benzo(thio)imidates, Benzo[d][1,3]thiazines and Quinazoline‐4‐thiones

Organic Synthesis with N‐Heterocyclic Carbenes of Indazole: Synthesis of Benzo(thio)imidates, Benzo[d][1,3]thiazines and Quinazoline‐4‐thiones

Atypical and Asymmetric 1,3‐P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes

syn‐anti Isomerizations and rearrangements

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