582-61-6Relevant academic research and scientific papers
Structure and reactivity of benzoylnitrene radical anion in the gas phase
Wijeratne, Neloni R.,Wenthold, Paul G.
, p. 9518 - 9522 (2007)
(Chemical Equation Presented) The open-shell benzoylnitrene radical anion, readily generated by electron ionization of benzoylazide, undergoes unique chemical reactivity with radical reagents and Lewis acids in the gas phase. Reaction with nitric oxide, NO, proceeds by loss of N2 and formation of benzoate ion. This novel reaction is also observed to occur with phenylnitrene anion, forming phenoxide. Similar reactivity was observed in the reaction between benzoylnitrene radical anion and NO2, forming benzoate ion and nitrous oxide. Electronic structure calculations indicate that the reaction has a high-energy barrier that is overcome by the energy released by bond formation. Benzoylnitrene radical anion also transfers oxygen anion to NO and NO2 as well as to CS2 and SO2. In contrast, phenylnitrene anion reacts with carbon disulfide by C+ or CS+ abstraction, forming S- or S2-. Electronic structure calculations indicate that benzoylnitrene in the ground state resembles a slightly polarized benzoate anion, but with a free radical localized on the nitrogen.
Synthesis of Cyclic N-Acyl Amidines by [3 + 2] Cycloaddition of N-Silyl Enamines and Activated Acyl Azides
Jo, Dong Geun,Joung, Seewon,Kim, Changeun,Lee, Sinjae,Yun, Sooyeon
supporting information, (2022/03/17)
In this study, we describe the synthesis of cyclic N-acyl amidines from readily available N-heteroarenes. The synthetic methodology utilized the versatile N-silyl enamine intermediates from the hydrosilylation of N-heteroarenes for the [3 + 2] cycloaddition reaction step. We evaluated various acyl azides and selected an electronically activated acyl azide, thereby achieving a reasonable yield of cyclic N-acyl amidines. We analyzed the relationship between the reactivity of each step and the electronic nature of substrates using in situ nuclear magnetic resonance spectroscopy. In addition, we demonstrated gram-scale synthesis using the proposed methodology.
Synthesis of Acyl Phosphoramidates Employing a Modified Staudinger Reaction
Currie, Iain,Sleebs, Brad E.
supporting information, p. 464 - 468 (2021/02/03)
A one-step synthesis of acyl phosphoramidates from a variety of functionalized acyl azides has been developed employing trimethylsilyl chloride as an activating agent in a modified Staudinger reaction. The methodology was further adapted to include the in situ generation of the acyl azides from a diverse selection of carboxylic acids and hydrazide starting synthons. The reaction scope was extended to include the synthesis of imidodiphosphates and the natural product Microcin C.
Unravelling the potency of triazole analogues for inhibiting α-synuclein fibrillogenesis andin vitrodisaggregation
Maqbool, Mudasir,Gadhavi, Joshna,Singh, Anju,Hivare, Pravin,Gupta, Sharad,Hoda, Nasimul
supporting information, p. 1589 - 1603 (2021/03/01)
A series of triazole-based compounds was synthesized using a click chemistry approach and evaluated for the inhibition of α-synuclein (α-syn) fibrillogenesis and its disaggregation. CompoundsTr3,Tr7,Tr12,Tr15, andTr16exhibited good effect in inhibiting α-
Deoxygenative Amination of Azine-N-oxides with Acyl Azides via [3 + 2] Cycloaddition
Ghosh, Prithwish,Han, Sang Hoon,Han, Sangil,Kim, Dongeun,Kim, In Su,Kim, Saegun,Kwon, Na Yeon,Mishra, Neeraj Kumar
, p. 2476 - 2485 (2020/03/13)
A transition-metal-free deoxygenative C-H amination reaction of azine-N-oxides with acyl azides is described. The initial formation of an isocyanate from the starting acyl azide via a Curtius rearrangement can trigger a [3 + 2] dipolar cycloaddition of polar N-oxide fragments to generate the aminated azine derivative. The applicability of this method is highlighted by the late-stage and sequential amination reactions of complex bioactive compounds, including quinidine and fasudil. Moreover, the direct transformation of aminated azines into various bioactive N-heterocycles illustrates the significance of this newly developed protocol.
Heterogeneous photocatalysis of azides: Extending nitrene photochemistry to longer wavelengths
Argüello, Juan E.,Lanterna, Anabel E.,Lemir, Ignacio D.,Scaiano, Juan C.
supporting information, p. 10239 - 10242 (2020/10/02)
The photodecomposition of azides to generate nitrenes usually requires wavelengths in the 300 nm region. In this study, we show that this reaction can be readily performed in the UVA region (368 nm) when catalyzed by Pd-decorated TiO2. In aqueous medium the reaction leads to amines, with water acting as the H source; however, in non-protic and non-nucleophilic media, such as acetonitrile, nitrenes recombine to yield azo compounds, while azirine-mediated trapping occurs in the presence of nucleophiles. The heterogeneous process facilitates catalyst separation while showing great chemoselectivity and high yields.
Synthesis of: N -methylated amines from acyl azides using methanol
Chakrabarti, Kaushik,Dutta, Kuheli,Kundu, Sabuj
supporting information, p. 5891 - 5896 (2020/08/21)
The transformation of acyl azide derivatives into N-methylamines was developed using methanol as the C1 source via the one-pot Curtius rearrangement and borrowing hydrogen methodology. Following this protocol, various functionalised N-methylated amines were synthesized using the (NNN)Ru(ii) complex from carboxylic acids via an acyl azide intermediate. Several kinetic studies and DFT calculations were carried out to support the mechanism and also to determine the role of the Ru(ii) complex and base in this transformation.
Copper-Catalyzed C(sp3)?H Amidation: Sterically Driven Primary and Secondary C?H Site-Selectivity
Bakhoda, Abolghasem (Gus),Jiang, Quan,Badiei, Yosra M.,Bertke, Jeffery A.,Cundari, Thomas R.,Warren, Timothy H.
supporting information, p. 3421 - 3425 (2019/02/14)
Undirected C(sp3)?H functionalization reactions often follow site-selectivity patterns that mirror the corresponding C?H bond dissociation energies (BDEs). This often results in the functionalization of weaker tertiary C?H bonds in the presence of stronger secondary and primary bonds. An important, contemporary challenge is the development of catalyst systems capable of selectively functionalizing stronger primary and secondary C?H bonds over tertiary and benzylic C?H sites. Herein, we report a Cu catalyst that exhibits a high degree of primary and secondary over tertiary C?H bond selectivity in the amidation of linear and cyclic hydrocarbons with aroyl azides ArC(O)N3. Mechanistic and DFT studies indicate that C?H amidation involves H-atom abstraction from R-H substrates by nitrene intermediates [Cu](κ2-N,O-NC(O)Ar) to provide carbon-based radicals R. and copper(II)amide intermediates [CuII]-NHC(O)Ar that subsequently capture radicals R. to form products R-NHC(O)Ar. These studies reveal important catalyst features required to achieve primary and secondary C?H amidation selectivity in the absence of directing groups.
Visible Light-Induced Regioselective Cycloaddition of Benzoyl Azides and Alkenes to Yield Oxazolines
Bellotti, Peter,Brocus, Julien,El Orf, Fatima,Selkti, Mohamed,K?nig, Burkhard,Belmont, Philippe,Brachet, Etienne
supporting information, p. 6278 - 6285 (2019/05/24)
Visible light catalysis allows the regioselective synthesis of oxazolines in high yields. The mild photosensitized manifold leverages the intermolecular formation of oxazolines with a wide functional group tolerance on both benzoyl azides and alkenes part
Aryl Azides as Forgotten Electrophiles in the Van Leusen Reaction: A Multicomponent Transformation Affording 4-Tosyl-1-arylimidazoles
Necardo, Cristiana,Alfano, Antonella Ilenia,Del Grosso, Erika,Pelliccia, Sveva,Galli, Ubaldina,Novellino, Ettore,Meneghetti, Fiorella,Giustiniano, Mariateresa,Tron, Gian Cesare
, p. 16299 - 16307 (2019/12/27)
Considering aryl azides as electrophilic partners for the TosMIC mediated Van Leusen reaction, a novel multicomponent synthesis of 4-tosyl-1-arylimidazoles is reported. In this transformation, two molecules of TosMIC participate in the reaction mechanism
