In Situ Generation of N-Triflylimino-λ3-iodanes: Application to Imidation of Phosphines and Catalytic α-Amidation of 1,3-Dicarbonyl Compounds

Sunagawa, Shun; Morisaki, Fumiya; Baba, Takafumi; Tsubouchi, Akira; Yoshimura, Atsushi; Miyamoto, Kazunori; Uchiyama, Masanobu; Saitô, Akio

doi:10.1021/acs.orglett.2c02264

Cited by 9 publications

(2 citation statements)

References 54 publications

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“…More stable than triflylimino-λ 3 -bromane are triflylimino-λ 3 -iodanes. The N-triflyl-substituted analogs of the latter, N-triflylimino-λ 3 -iodanes ArI=NTf, were synthesized by the reaction of iodosobenzenes ArI=O with triflamide as late as in 2022 and used for amidation or imidation of phosphines and 1,3-diketones [26]. However, in our recent work [27], we found no aziridines in the reaction of styrene with triflamide and iodosobenzene in the presence of iodine and CuCl.…”

Section: Introductionmentioning

confidence: 97%

The Reactions of Alkenes with Phenyl-N-triflylimino-λ3-iodane: Solvent and Oxidant Impact

Moskalik,

Ganin,

Shainyan

2023

IJMS

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The reactions of alkenes with phenyl-N-triflylimino-λ3-iodane PhI=NTf (1) have been studied in different conditions. In methylene chloride, in the presence of N-halosuccinimides, the products of mono and bis-triflamidation were obtained. In MeCN, the product of bromotriflamidation (with NBS) with solvent interception or of bis-triflamidation (with NIS) is formed. The reaction with trans-stilbene in acetonitrile with NBS gave rise to cyclization to 2-methyl-4,5-diphenyl-1-triflyl-4,5-dihydro-1H-imidazole. In contrast, with NIS as an oxidant, both in CH2Cl2 and MeCN, the major product was 2,3-diphenyl-1-triflylaziridine formed in good yield. With NBS, aziridine is also formed but as a minor product, the major one being a mixture of diastereomers of the product of bromotriflamidation. The reaction of compound 1 with vinylcyclohexane in methylene chloride affords the mixtures of regioisomers of the products of halotriflamidation, whereas in acetonitrile, the products of solvent interception and cyclization to the imidazoline are formed. A mechanism explaining the formation of all isolated products is proposed.

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Section: Introductionmentioning

confidence: 97%

The Reactions of Alkenes with Phenyl-N-triflylimino-λ3-iodane: Solvent and Oxidant Impact

Moskalik,

Ganin,

Shainyan

2023

IJMS

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“…Conventionally, iminophosphoranes can be synthesized through Staudinger reduction − or by reacting phosphines with iminoiodanes (Scheme a,b). − Alternatively, Kirsanov , − Appel -type, − or Mitsunobu -type − reactions can be performed to generate an electrophilic phosphine intermediate in situ, which is then trapped by the nitrogen precursor (Scheme c–e).…”

Section: Introductionmentioning

confidence: 99%

Efficient and Sustainable Electrosynthesis of N-Sulfonyl Iminophosphoranes by the Dehydrogenative P–N Coupling Reaction

Bieniek,

Nater,

Eberwein

et al. 2024

JACS Au

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Iminophosphoranes are commonly used reagents in organic synthesis and are, therefore, of great interest. An efficient and sustainable iodide-mediated electrochemical synthesis of Nsulfonyl iminophosphoranes from readily available phosphines and sulfonamides is reported. This method features low amounts of supporting electrolytes, inexpensive electrode materials, a simple galvanostatic setup, and high conversion rates. The broad applicability could be demonstrated by synthesizing 20 examples in yields up to 90%, having diverse functional groups including chiral moieties and biologically relevant species. Furthermore, electrolysis was performed on a 20 g scale and could be run in repetitive mode by recycling the electrolyte, which illustrates the suitability for large-scale production. A reaction mechanism involving electrochemical mediation by the iodide-based supporting electrolyte is proposed, completely agreeing with all of the results.

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Recent trends in the chemistry of triflamides

Shainyan

2023

Tetrahedron

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In Situ Generation of N-Triflylimino-λ³-iodanes: Application to Imidation of Phosphines and Catalytic α-Amidation of 1,3-Dicarbonyl Compounds

Cited by 9 publications

References 54 publications

The Reactions of Alkenes with Phenyl-N-triflylimino-λ3-iodane: Solvent and Oxidant Impact

The Reactions of Alkenes with Phenyl-N-triflylimino-λ3-iodane: Solvent and Oxidant Impact

Efficient and Sustainable Electrosynthesis of N-Sulfonyl Iminophosphoranes by the Dehydrogenative P–N Coupling Reaction

Recent trends in the chemistry of triflamides

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