Ni-Catalyzed Carboxylation of Aziridines en Route to β-Amino Acids

Davies, Jacob; Janssen‐Müller, Daniel; Zimin, Dmitry P.; Day, Craig S.; Yanagi, Tomoyuki; Elfert, Jonas; Martı́n, Rubén

doi:10.1021/jacs.1c01916

Cited by 68 publications

(27 citation statements)

References 57 publications

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“…Taking into consideration the influence exerted by sterically encumbered 2,2-bipyridine ligands on reactivity, 48 we turned our attention to investigating the generality of accessing reduced polypyridine-Mg species other than 3 , as it might pave the way for future synthetic applications. To this end, an otherwise similar route to that shown for 3 was followed with more sterically encumbered L2 (6,6′-dimethyl-4,4′-diphenyl-2,2′-bipyridine), using ( L2 )NiBr 2 ( 4 ) as a precursor ( Figure 4 ).…”

Section: Resultsmentioning

confidence: 99%

Room-Temperature-Stable Magnesium Electride via Ni(II) Reduction

et al. 2022

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Herein, we report the synthesis of highly reduced bipyridyl magnesium complexes and the first example of a stable organic magnesium electride supported by quantum mechanical computations and X-ray diffraction. These complexes serve as unconventional homogeneous reductants due to their high solubility, modular redox potentials, and formation of insoluble, non-coordinating byproducts. The applicability of these reductants is showcased by accessing low-valent (bipy) 2 Ni(0) species that are challenging to access otherwise.

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Section: Resultsmentioning

confidence: 99%

Room-Temperature-Stable Magnesium Electride via Ni(II) Reduction

et al. 2022

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“…Metal-catalyzed cross-coupling of aziridine often results in ring opening products 16 – 24 . In contrast, we observed Ni-catalyzed C–N coupling to generate N -arylaziridines in which the aziridine ring is conserved in the product.…”

Section: Resultsmentioning

confidence: 99%

“…The resulting N -protected aziridines can be challenging to utilize in downstream N -functionalization chemistry. For example, exposure of N -sulfonyl aziridines to metal-catalyzed cross-coupling conditions typically results in aziridine opening, not N -functionalization 16 – 24 . N–H aziridines can be accessed by either deprotection of N -protected aziridines 25 – 27 or by direct synthesis of olefinic precursors (Fig.…”

Section: Introductionmentioning

confidence: 99%

N-Aminopyridinium reagents as traceless activating groups in the synthesis of N-Aryl aziridines

et al. 2022

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N-functionalized aziridines, which are both useful intermediates and important synthetic targets, can be envisioned as arising from the addition of nitrenes (i.e., NR fragments) to olefinic substrates. The exceptional reactivity of most nitrenes, in particular with respect to unimolecular decomposition, prevents general application of nitrene-transfer to the synthesis of N-functionalized aziridines. Here we demonstrate N-aryl aziridine synthesis via 1) olefin aziridination with N-aminopyridinium reagents to afford N-pyridinium aziridines followed by 2) Ni-catalyzed C–N cross-coupling of the N-pyridinium aziridines with aryl boronic acids. The N-pyridinium aziridine intermediates also participate in ring-opening chemistry with a variety of nucleophiles to afford 1,2-aminofunctionalization products. Mechanistic investigations indicate aziridine cross-coupling proceeds via a noncanonical mechanism involving initial aziridine opening promoted by the bromide counterion of the Ni catalyst, C–N cross-coupling, and finally aziridine reclosure. Together, these results provide new opportunities to achieve selective incorporation of generic aryl nitrene equivalents in organic molecules.

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“…We speculate that there are some reactions between CO 2 and Lewis base sites of the carbon matrix in the presence of Ni atoms to form a new carbon skeleton, as reported by Martin. 35 The new carbon skeleton will liberate CO and NH 3 intensively at above 800 °C, accordingly, forming a new mesopore structure. Temperature programmed desorption (TPD) measurements have been performed over the Ni/NC catalyst under CO 2 and Ar atmospheres to confirm the proposed formation mechanism.…”

Section: Effect Of Pyrolysis Temperaturementioning

confidence: 99%