O-Benzoylhydroxylamines: A Versatile Electrophilic Aminating Reagent for Transition Metal-Catalyzed C–N Bond-Forming Reactions

Mohite, Sachin Balaso; Bera, Milan; Kumar, Vijay; Karpoormath, Rajshekhar; Shaik, Baji Baba; Kumbhar, Arjun

doi:10.1007/s41061-022-00414-5

Cited by 13 publications

(5 citation statements)

References 108 publications

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“…We began our study by investigating the hydroamination with O -benzoyl hydroxylpiperidine 1 and α-methylstyrene 3 (Figure ). We chose O -benzoyl hydroxylamines , because they possess a weak N–O bond which can be mesolytically cleaved upon reduction to produce the ARC and because they are easily generated from dialkyl amines in one step. Because of their low reduction potentials (e.g., for O -benzoyl hydroxylpiperidine, E 1/2 = −1.88 V vs SCE in MeCN), reduced flavin hydroquinone (FMN hq ) in the ground-state would be unable to reduce O -benzoyl hydroxylamines; however, we surmised that the lower reduction potential afforded to excited-state FMN hq * would be sufficient to reduce hydroxylamines .…”

Section: Resultsmentioning

confidence: 99%

Photoenzymatic Asymmetric Hydroamination for Chiral Alkyl Amine Synthesis

Harrison,

Jiang,

Zhang

et al. 2024

J. Am. Chem. Soc.

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Chiral alkyl amines are common structural motifs in pharmaceuticals, natural products, synthetic intermediates, and bioactive molecules. An attractive method to prepare these molecules is the asymmetric radical hydroamination; however, this approach has not been explored with dialkyl amine-derived nitrogen-centered radicals since designing a catalytic system to generate the aminium radical cation, to suppress deleterious side reactions such as α-deprotonation and H atom abstraction, and to facilitate enantioselective hydrogen atom transfer is a formidable task. Herein, we describe the application of photoenzymatic catalysis to generate and harness the aminium radical cation for asymmetric intermolecular hydroamination. In this reaction, the flavin-dependent ene-reductase photocatalytically generates the aminium radical cation from the corresponding hydroxylamine and catalyzes the asymmetric intermolecular hydroamination to furnish the enantioenriched tertiary amine, whereby enantioinduction occurs through enzyme-mediated hydrogen atom transfer. This work highlights the use of photoenzymatic catalysis to generate and control highly reactive radical intermediates for asymmetric synthesis, addressing a long-standing challenge in chemical synthesis.

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Section: Resultsmentioning

confidence: 99%

Photoenzymatic Asymmetric Hydroamination for Chiral Alkyl Amine Synthesis

Harrison,

Jiang,

Zhang

et al. 2024

J. Am. Chem. Soc.

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“…Recently, metal hydride-catalyzed hydrofunctionalization of alkenes has attracted considerable attention. − It has been reported that some NiH complexes demonstrate robust catalytic activity for enantioselective C–N bond-forming processes, − wherein O-benzoyl hydroxylamines (BzO–NR 2 ) are used as electrophilic amination reagent which is compatible to the presence of reductant reagents in the reaction system . Accordingly, we commenced our studies on the Ni-catalyzed model reaction of phenylbutadiene 1a and morpholino benzoate 2a , and a preliminary parameter survey revealed that the reaction was best run at rt in 2-Me-THF with Ni(COD) 2 as the Ni source in the presence of trimethoxysilane and K 2 CO 3 (for details, see SI).…”

Section: Resultsmentioning

confidence: 99%

Nickel Catalyzed Enantioselective 1,4-Hydroamination of 1,3-Dienes

Wang,

Wang

et al. 2024

J. Am. Chem. Soc.

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“…Gratifyingly, Berman and Campbell's work helped Oacyl hydroxylamines to become indispensable reagents for the direct delivery of the R 2 N(+) and RHN(+) synthons in a wide range of catalytic applications throughout laboratories globally. While the full breadth of these transformations is beyond the scope of this Account and has recently been reviewed, 17,18 a summation of key advances will be discussed. The scope of carbon nucleophiles was expanded to include alkyl 19 and aryl boronates 20,21 and silyl ketene acetals.…”

Section: Broader Usementioning

confidence: 99%

Development of New Reactions Driven by N–O Bond Cleavage: from O-Acyl Hydroxylamines to Tetrodotoxin

Johnson¹,

Robins²

2023

Synlett

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This Account describes new reactions that have been developed in the Johnson laboratories at UNC Chapel Hill enabled by considerations of N–O bond cleavage. Three main case studies are highlighted: the metal-catalyzed electrophilic amination of O-acyl hydroxyl amines, multihetero-Cope rearrangements driven by O–N bond breakage, and merged dearomatization/N=O cycloadditions for the synthesis of complex 4-aminocyclohexanols such as those found in the natural product tetrodotoxin.1 Introduction2 Electrophilic Amination3 Multihetero-Cope Rearrangements4 Progress toward a Total Synthesis of (–)-Tetrodotoxin5 Conclusion

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O-Benzoylhydroxylamines: A Versatile Electrophilic Aminating Reagent for Transition Metal-Catalyzed C–N Bond-Forming Reactions

Cited by 13 publications

References 108 publications

Photoenzymatic Asymmetric Hydroamination for Chiral Alkyl Amine Synthesis

Photoenzymatic Asymmetric Hydroamination for Chiral Alkyl Amine Synthesis

Nickel Catalyzed Enantioselective 1,4-Hydroamination of 1,3-Dienes

Development of New Reactions Driven by N–O Bond Cleavage: from O-Acyl Hydroxylamines to Tetrodotoxin

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