83020-38-6Relevant academic research and scientific papers
An umpolung approach toward N-aryl nitrone construction: A phosphine-mediated addition of 1,2-dicarbonyls to nitroso electrophiles
Chavannavar, Aditi P.,Oliver, Allen G.,Ashfeld, Brandon L.
, p. 10853 - 10856 (2014)
An umpolung approach toward nitrone construction utilizing a phosphine-mediated addition of 1,2-dicarbonyls to nitroso compounds is reported. The reaction exhibits a high degree of chemoselectivity and provides direct access to isoxazolidines, imines, and
Construction of α-methoxyimidoyl ketonitrones: Via phosphite-mediated addition of α-keto N-tert -butanesulfinyl imidates to nitrosoarenes
Feng, Jie,Ma, Peng-Ju,Zeng, Yong-Ming,Xu, Yan-Jun,Lu, Chong-Dao
, p. 2882 - 2885 (2018)
A dimethyl phosphite-mediated addition of α-keto N-tert-butanesulfinyl imidates to nitrosoarenes was developed. Nitrosoarenes were successfully used as electrophiles to trap aza-enolate intermediates that were generated from nucleophilic addition of deprotonated phosphite to α-keto N-tert-butanesulfinyl imidates and following phospha-Brook rearrangement, allowing efficient construction of ketonitrones with excellent (Z)-geometries.
Visible-light-promoted nitrone synthesis from nitrosoarenes under catalyst- and additive-free conditions
Cai, Bao-Gui,Li, Lin,Xiao, Wen-Jing,Xu, Guo-Yong,Xuan, Jun
, p. 823 - 829 (2021/06/15)
A green and sustainable nitrone formation reaction via visible-light-promoted reaction of aryl diazoacetates with nitrosoarenes is described. This protocol exhibits good functional group tolerance and broad substrate scope for both aryl diazoacetates with nitrosoarenes. Comparing the reported methods for the synthesis of nitrones from nitrosoarenes, the reaction described herein occurs under sole visible-light irradiation without the need of any catalysts and additives. Graphic abstract: [Figure not available: see fulltext.]
Single-Step Approach toward Nitrones via Pyridinium Ylides: The DMAP-Catalyzed Reaction of Benzyl Halides with Nitrosoarenes
Jung, Yeonghun,Hong, Jee Eun,Kwak, Jae-Hwan,Park, Yohan
, p. 6343 - 6350 (2021/05/29)
A single-step approach is reported for the preparation of nitrones from benzyl halides and nitrosoarenes via pyridinium ylides, utilizing 4-dimethylaminopyridine (DMAP) catalyst and mild reaction conditions (Li2CO3, dimethylacetamide, and room temperature). The reaction provides both keto-and aldonitrones in high yields with a wide scope for benzyl halides and nitrosoarenes. In the same reaction system, 2-methyl-2-nitrosopropane, which does not have an aryl group, also affords the corresponding N-tert-butyl nitrones from primary benzyl bromides that have an electron-withdrawing group. As an application of the reaction, methyl 2-bromo-2-phenylacetate was used to prepare the corresponding isoxazolidine by a sequential one-pot synthesis.
Nitrone/Imine Selectivity Switch in Base-Catalysed Reaction of Aryl Acetic Acid Esters with Nitrosoarenes: Joint Experimental and Computational Study
Volpe, Chiara,Meninno, Sara,Roselli, Angelo,Mancinelli, Michele,Mazzanti, Andrea,Lattanzi, Alessandra
supporting information, p. 5457 - 5466 (2020/10/12)
Herein we report a mild and diastereoselective access to ketonitrones by reacting easily available aryl acetic acid esters and other active methylene compounds, with nitrosoarenes under catalytic loading of 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) at room temperature. Depending on the substitution pattern and nature of the aryl moiety, a switch toward the formation of imines can be observed. The mechanistic framework is put to scrutiny by experimental and theoretical studies, pointing to the formation of a nitroso aldol intermediate, whose fate toward one of the competing pathways, namely hydride transfer or elimination, would depend upon the NOH/CHα relative acidities. (Figure presented.).
Novel Photocycloadditions of Electron-Deficient Nitrones to 2-Methyl-2-butene
Sehgal, R. K.,Griffin, G. W.
, p. 513 - 517 (2007/10/02)
In order to decrease the ground state reactivity and increase their potential for cycloadditions, cyano- and methoxycarbonyl-substituted nitrones 1a and 1b, respectively, were prepared and irradiated in the presence of electron-rich alkenes such as 2 to afford the corresponding oxazolidines in which the oxygen atom becomes attached to the least substituted terminus of the olefin and nitrogen attaches the more highly substituted counterpart.While the oxazolidines 12a and 12b obtained from 1b, via the intermediacy of oxaziridine(s) 15 and subsequent N-O bond scission, are isolated and characterized, the oxazolidine(s) 18 formed by cycl ization of 1a are more labile and may undergo ionization to the stabilized oxazolinium ion 19 followed by nucleophilic attack by cyanide ion with accompanying ring opening to afford 6.A sequential diradical mechanism is proposed to rationalize the formation of the observed photoproducts 5 and 6.
