Influence of solvent on diazoalkane-alkyldiazonium ion equilibriums in amine deaminations

Friedman, Lester; Jurewicz, Anthony T.; Bayless, John H.

doi:10.1021/ja01035a032

Cited by 16 publications

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“…Although, in analogy to aromatic amines, there are numerous reports attempting to functionalise electronically non-biased primary aliphatic amines by diazotisation, formation of highly reactive alkyldiazonium intermediates rendered those reactions inefficient and made them suffer from poor functional group tolerance and low yields. [37][38][39][40][41][42] We hypothesized that substitution of conventional mineral acids, such as HCl and HBF 4 , used for the synthesis of aromatic diazonium salts, by a mild organic Lewis acid might suppress the unproductive formation of the high-energy alkyl diazonium species and thus unlock a divergent reaction outcome (Fig. 1d).…”

Section: Resultsmentioning

confidence: 99%

Deaminative coupling of benzylamines and arylboronic acids

2023

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Section: Resultsmentioning

confidence: 99%

Deaminative coupling of benzylamines and arylboronic acids

2023

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“…However a reversible β-hydride elimination event followed by a slow dissociation of imine prior to TBE hydrogenation could not be eliminated out of hand. This scenario was examined by monitoring the dehydrogenation of the 1-NH 2 i Bu isotopologue, [C 6 H 3 -2,6-(OP t Bu 2 ) 2 ]Ir(ND 2 i Bu) . If the β-hydride elimination event were reversible, the deuterium labels on the amino position would be expected to scramble with those protons on the neighboring carbon center prior to nitrile formation .…”

Section: Resultsmentioning

confidence: 99%

Kinetics and Mechanism of Iridium-Catalyzed Dehydrogenation of Primary Amines to Nitriles

Bernskoetter

Brookhart

2008

Organometallics

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A family of primary amines has been catalytically dehydrogenated to nitriles by [C6H3-2,6-(OP t Bu2)2]IrH2 using tert-butylethylene as a hydrogen acceptor. The catalytic mechanism has been investigated by a series of kinetic and isotopic labeling experiments, in addition to the isolation of intermediates along the reaction pathway. The turnover frequency exhibits a first-order dependence on the concentration of amine, an inverse first-order dependence on nitrile, and a zero-order dependence on tert-butylethylene. The mechanism of amine dehydrogenation is proposed to proceed from an iridium(I) nitrile complex, the catalyst resting state, via two preturnover limiting equilibria, followed by a slow β-hydride elimination event from a transient iridium(III) amido hydride species. Measuring rate constants for the stoichiometric dehydrogenation of isobutylamine over a 41 °C temperature range established activation parameters for β-hydride elimination of ΔH ⧧ 24.8(9) kcal/mol and ΔS ⧧ = −10(2) eu. Dehydrogenation of a series of para-substituted benzyl amines indicated enhanced conversions to nitriles for substrates bearing electron-donating substituents.

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“…Various strategies have therefore been explored to favor C–N activation via prefunctionalization (Scheme A). Early examples include diazonium salts, , but these highly reactive intermediates prone to elimination typically lead to undesired side reactions and poor functional group tolerance. An interrupted diazotization strategy was recently leveraged to functionalize α-primary benzylamines with boronic acids .…”

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Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

et al. 2023

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While being among the most common functional handles present in organic molecules, amines are a widely underutilized linchpin for C–C bond formation. To facilitate C–N bond cleavage, large activating groups are typically used but result in the generation of stoichiometric amounts of organic waste. Herein, we report an atom-economical activation of benzylic primary amines relying on the sulfur(VI) fluoride exchange (SuFEx) click chemistry and the aza-Ramberg–Bäcklund reaction. This two-step sequence allows the high-yielding generation of 1,2-dialkyldiazenes from primary amines via loss of SO2. Excitation of the diazenes with blue light and an Ir photocatalyst afford radical pairs upon expulsion of N2, which can be coaxed into the formation of C(sp3)–C(sp2) bonds upon diffusion and capture by a Ni catalyst. This arylative strategy relying on a traceless click approach was harnessed in a variety of examples, and its mechanism was investigated.

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Influence of solvent on diazoalkane-alkyldiazonium ion equilibriums in amine deaminations

Cited by 16 publications

References 0 publications

Deaminative coupling of benzylamines and arylboronic acids

Deaminative coupling of benzylamines and arylboronic acids

Kinetics and Mechanism of Iridium-Catalyzed Dehydrogenation of Primary Amines to Nitriles

Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

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