ChemInform Abstract: Mode of Action and Biosynthesis of the Azabicycle‐Containing Natural Products Azinomycin and Ficellomycin

Foulke‐Abel, Jennifer; Agbo, Hillary; Zhang, Huitu; Mori, Shogo; Watanabe, Coran M. H.

doi:10.1002/chin.201128266

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“…Catalytic aziridination has made noteworthy strides in the past decade due to the development of many new catalysts. [1][2][3][4][5][6][7][8] These advances are significant since aziridines not only are found in natural products [9][10][11] but also are critical intermediates that can be ringopened stereospecifically or transformed into a plethora of more complex heterocyclic ring systems via ring expansion. [12][13][14][15][16][17][18] For example, Kang 19 and Ghorai 20 have showcased chiral ring-opening reactions with meso aziridines, while Zhao, Chai, and Wang developed the first pyrroloindoline synthesis from aziridines and indoles.…”

Section: Introductionmentioning

confidence: 99%

Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

et al. 2019

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A combined computational and experimental study was undertaken to elucidate the mechanism of catalytic C 2 + N 1 aziridination supported by tetracarbene iron complexes. Three specific aspects of the catalytic cycle were addressed. First, how do organic azides react with different iron catalysts and why are alkyl azides ineffective for some catalysts? Computation of the catalytic pathway using density functional theory (DFT) revealed that an alkyl azide needs to overcome a higher activation barrier than an aryl azide to form an iron imide, and the activation barrier with the firstgeneration catalyst is higher than the activation barrier with the second-generation variant. Second, does the aziridination from the imide complex proceed through an open-chain radical intermediate that can change stereochemistry or, instead, via an azametallacyclobutane intermediate that retains stereochemistry? DFT calculations show that the formation of aziridine proceeds via the openchain radical intermediate, which qualitatively explains the formation of both aziridine diastereomers as seen in experiments. Third, how can the formation of the side product, a metallotetrazene, be prevented, which would improve the yield of aziridine at lower alkene loading? DFT and experimental results demonstrate that sterically bulky organic azides prohibit formation of the metallotetrazene and, thus, allow lower alkene loading for effective catalysis. These multiple insights of different aspects of the catalytic cycle are critical for developing improved catalysts for C 2 + N 1 aziridination.

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Section: Introductionmentioning

confidence: 99%

Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

et al. 2019

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ChemInform Abstract: Mode of Action and Biosynthesis of the Azabicycle‐Containing Natural Products Azinomycin and Ficellomycin

Abstract: Azinomycin and Ficellomycin -[58 refs.]. -(FOULKE-ABEL, J.; AGBO, H.; ZHANG, H.; MORI, S.; WATANABE*, C. M. H.; Nat. Prod. Rep. 28 (2011) 4, 693-704, http://dx.doi.org/10.1039/c0np00049c ; Dep. Chem., Tex. A&M Univ., College Station, TX 77843, USA; Eng.) -Lindner 28-266

Cited by 1 publication

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Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

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ChemInform Abstract: Mode of Action and Biosynthesis of the Azabicycle‐Containing Natural Products Azinomycin and Ficellomycin

Abstract: Azinomycin and Ficellomycin -[58 refs.]. -(FOULKE-ABEL, J.; AGBO, H.; ZHANG, H.; MORI, S.; WATANABE*, C. M. H.; Nat. Prod. Rep. 28 (2011) 4, 693-704, http://dx.doi.org/10.1039/c0np00049c ; Dep. Chem., Tex. A&M Univ., College Station, TX 77843, USA; Eng.) -Lindner 28-266

Cited by 1 publication

References 1 publication

Elucidation of the Reaction Mechanism of C2 + N1 Aziridination from Tetracarbene Iron Catalysts

Elucidation of the Reaction Mechanism of C2 + N1 Aziridination from Tetracarbene Iron Catalysts

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Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts

Elucidation of the Reaction Mechanism of C₂ + N₁ Aziridination from Tetracarbene Iron Catalysts