Ni-Catalyzed Oxygen Transfer from N<sub>2</sub>O onto sp<sup>3</sup>-Hybridized Carbons

Ni, Shengyang; Vaillant, Franck Le; Calbet, Ana Mateos; Martı́n, Rubén; Cornellà, Josep

doi:10.1021/jacs.2c06227

Cited by 13 publications

(4 citation statements)

References 58 publications

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“…To the best of our knowledge, this is the first observation that hydrogen peroxide can act as an oxygen atom transfer reagent to afford an isolable oxygenated Ni complex, in an oxygenase-like process. Notably, N 2 O is usually required as the oxygen atom transfer reagent for Ni complexes, with much longer reaction times being necessary. − In our case, the formation of the cycloether product 7 could be generated upon the oxidatively induced reductive elimination from the nickelacycloether 11 . Alternatively, oxidation of 11 followed by a second C–O reductive elimination in the presence of hydroxide could lead to the formation of 2-(1-hydroxy-2-methylpropan-2-yl)phenol ( 12 ), which was indeed observed under aerobic oxidation conditions (Table S6).…”

Section: Resultsmentioning

confidence: 89%

Nickel–Carbon Bond Oxygenation with Green Oxidants via High-Valent Nickel Species

Kim

Baik

et al. 2023

J. Am. Chem. Soc.

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Described herein is the synthesis of the Ni II complex ( t BuMe 2 tacn)Ni II (cycloneophyl) ( t BuMe 2 tacn = 1-tertbutyl-4,7-dimethyl-1,4,7-triazacyclononane, cycloneophyl = −CH 2 CMe 2 -o-C 6 H 4 −) and its reactivity with dioxygen and peroxides. The new t BuMe 2 tacn ligand is designed to enhance the oxidatively induced bond-forming reactivity of high-valent Ni intermediates. Tunable chemoselectivity for Csp 2 −O vs Csp 2 − Csp 3 bond formation was achieved by selecting the appropriate solvent and reaction conditions. Importantly, the use of cumene hydroperoxide and meta-chloroperbenzoic acid suggests a heterolytic O−O bond cleavage upon reaction with ( t BuMe 2 tacn)Ni II (cycloneophyl). Mechanistic studies using isotopically labeled H 2 O 2 support the generation of a high-valent Ni-oxygen species via an inner-sphere mechanism and subsequent reductive elimination to form the Csp 2 −O bond. Kinetic studies of the exceptionally fast Csp 2 −O bond-forming reaction reveal a first-order dependence on both ( t BuMe 2 tacn)Ni II (cycloneophyl) and H 2 O 2 , and thus an overall second-order reaction. Eyring analysis further suggests that the oxidation of the Ni II complex by H 2 O 2 is the rate-determining step, which can be modulated by the presence of coordinating solvents. Moreover, computational studies fully support the conclusions drawn from experimental results. Overall, this study reveals for the first time the ability to control the oxidatively induced C−C vs C−O bond formation reactions at a Ni center. Importantly, the described system merges the known organometallic reactivity of Ni with the biomimetic oxidative transformations resembling oxygenases and peroxidases, and involving high-valent metal-oxygen intermediates, which is a novel approach that should lead to unprecedented oxidative catalytic transformations.

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Section: Resultsmentioning

confidence: 89%

Nickel–Carbon Bond Oxygenation with Green Oxidants via High-Valent Nickel Species

Kim

Baik

et al. 2023

J. Am. Chem. Soc.

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“…In 2022, Cornella exposed a catalytic synthesis of naphthenols utilizing the potential of N 2 O as an O transfer agent onto sp 3 ‐hybrid carbons (Scheme 45). [47] Attractively, the strategy was extended to the challenging catalytic synthesis of C(sp 3 )−O bonds by using N 2 O as O atom transfer (OAT) reagent and forming optically active dihydrobenzofuranols and indanols. Compared with indanols, dihydrobenzofuranols performed better enantioselectivity.…”

Section: Domino Heck Reactionmentioning

confidence: 99%

Recent Progress in Asymmetric Domino Intramolecular Cyclization/Cascade Reactions of Substituted Olefins

Zou

Gao

Zhang

et al. 2023

Chemistry An Asian Journal

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The domino cyclization/coupling strategy is one of the most effective methods to produce cyclized and multi‐functionalized compounds from olefins, which has attracted huge attention from chemists and biochemists especially for its considerable potential of enantiocontrol. Nowadays, more and more studies are developed to achieve difunctionalization of substituted olefins through an asymmetric domino intramolecular cyclization/cascade reaction, which is still an elegant choice to accomplish several synthetic ideas such as complex natural products and drugs. This review surveys the recent advances in this field through reaction type classification. It might serve as useful knowledge desktop for the community and accelerate their research.

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“…Although the reuse of carbon sources such as carbon dioxide or methane are well documented, [1,2] the upgrading of nitrous oxide (N 2 O), another major contributor to the global warming, [3,4] is a research field of prime importance considering the fact that the emissions are steeply increasing, with an estimated rate of 2 % per decade, owing to human activities (for instance agriculture, biomass burning, production of nitric and adipic acids [5] ). This compound effectively constitutes an available and cheap oxygen source, only releasing benign dinitrogen (N 2 ), [6] but with quite limited applications as oxidant in organic synthesis owing to the high temperatures (140–350 °C) and pressures (50–200 bar) required for its activation [7] . Moreover, nitrous oxide (N 2 O) has already proved to be a more selective oxidative agent than dioxygen (O 2 ) in the catalytic oxidation of methane into methanol under high temperature activation, [8] or for the synthesis of air sensitive compounds [9] .…”

Section: Introductionmentioning

confidence: 99%

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N₂O Atmosphere**

Delaunay,

Denicourt‐Nowicki,

Roucoux

2023

ChemCatChem

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In a climate change context, N2O contributes to global warming with CO2 and CH4. As an inert molecule, its upgrading as oxidant still constitutes a challenge in chemical synthesis. Here, the synthesis of imines was unprecedently performed using nitrous oxide (N2O) as a novel and highly selective oxidative agent for the photocatalytic homo‐coupling of amines. In a similar way, unsymmetric imines were produced through cross‐coupling of amines with alcohols. Promisingly, this greenhouse gas showed excellent performances towards the target reactions when photocatalytically activated at atmospheric pressure, with silver photodeposited on titanium dioxide as catalyst. Relevantly, reactions under N2O atmosphere exhibited high conversion rates and turn‐over frequencies, and higher selectivities than the ones carried out under a dioxygen atmosphere. Mechanisms for both reactions were detailed, showing the release of nitrogen and water as benign by‐products.

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Ni-Catalyzed Oxygen Transfer from N₂O onto sp³-Hybridized Carbons

Cited by 13 publications

References 58 publications

Nickel–Carbon Bond Oxygenation with Green Oxidants via High-Valent Nickel Species

Nickel–Carbon Bond Oxygenation with Green Oxidants via High-Valent Nickel Species

Recent Progress in Asymmetric Domino Intramolecular Cyclization/Cascade Reactions of Substituted Olefins

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N₂O Atmosphere**

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Ni-Catalyzed Oxygen Transfer from N2O onto sp3-Hybridized Carbons

Cited by 13 publications

References 58 publications

Nickel–Carbon Bond Oxygenation with Green Oxidants via High-Valent Nickel Species

Nickel–Carbon Bond Oxygenation with Green Oxidants via High-Valent Nickel Species

Recent Progress in Asymmetric Domino Intramolecular Cyclization/Cascade Reactions of Substituted Olefins

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N2O Atmosphere**

Contact Info

Product

Resources

About

Ni-Catalyzed Oxygen Transfer from N₂O onto sp³-Hybridized Carbons

Unprecedented Selective Synthesis of Imines by Photocatalytic Oxidative Coupling of Primary Amines under N₂O Atmosphere**