Benzhydrylamines via base-mediated intramolecular sp(3) C-arylation of N-benzyl-2-nitrobenzenesulfonamides--advanced intermediates for the synthesis of nitrogenous heterocycles.

ACS Comb Sci

Department of Organic Chemistry, Institute of Molecular and Translational Medicine, Faculty of Science, Palacký University, 17. Listopadu 12, 771 46 Olomouc, Czech Republic.

Published: October 2014

N-Benzyl-2-nitrobenzenesulfonamides underwent base-mediated intramolecular arylation at the benzyl sp(3) carbon to yield benzhydrylamines. The presence of electron withdrawing groups on the aromatic ring of the benzyl group was required to facilitate the C-arylation. Unsymmetrically substituted benzhydrylamines are advanced intermediates toward nitrogenous heterocycles, as exemplified in the syntheses of indazole oxides and quinazolines.

Download full-text PDF

Source
http://dx.doi.org/10.1021/co500098yDOI Listing

Publication Analysis

Top Keywords

base-mediated intramolecular
8
nitrogenous heterocycles
8
benzhydrylamines base-mediated
4
intramolecular sp3
4
sp3 c-arylation
4
c-arylation n-benzyl-2-nitrobenzenesulfonamides--advanced
4
n-benzyl-2-nitrobenzenesulfonamides--advanced intermediates
4
intermediates synthesis
4
synthesis nitrogenous
4
heterocycles n-benzyl-2-nitrobenzenesulfonamides
4

Similar Publications

This study presents the design and application of intramolecular arylogous nitroaldol (Henry) condensation. A transition metal-free, base-mediated reaction of -heteroatom-substituted aryl aldehydes/ketones and 2-nitrobenzyl (pseudo)halides has been developed to access a wide range of 2-(2-nitroaryl)benzofuran/2-(2-nitroaryl)indole derivatives in high yields. The reaction appears to proceed through -/-benzylation and intramolecular arylogous nitroaldol condensation.

View Article and Find Full Text PDF

Base-Mediated Regioselective [3 + 3] Annulation of Alkylidene Malononitriles with Trifluoromethyl Alkenes via Dual C-F Bond Cleavage.

Org Lett

September 2024

State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, College of Chemistry, Xinjiang University, Urumqi 830046, Xinjiang, P. R. China.

A base-mediated regioselective [3 + 3] annulation of alkylidene malononitriles with trifluoromethyl alkenes was described. The reaction proceeds through sequential intermolecular S2' and intramolecular SV-type cyclization by cleaving dual C-F bonds in a trifluoromethyl group, which discriminate multiple carbon-nucleophilic sites using a single base. Various bicycles bearing a monofluorocyclohexene motif were assembled from readily available starting materials under mild conditions via a one-pot cascade approach.

View Article and Find Full Text PDF

Decarboxylative C(sp2)-heteroatom cross-coupling reactions hold extraordinary potential for the sustainable preparation of biologically active scaffolds. Herein, we report a copper sulfate/1,10-phenathroline catalytic system for the decarboxylative intramolecular C(sp2)-O, C(sp2)-S, and C(sp2)-N coupling reactions leading to the construction of a series of benzo[]furans, benzo[]thiophenes, and indole derivatives from the corresponding coumarins, thiocoumarins, or quinolones, respectively. Our mechanistic study based on benzo[]furan formation suggests a three-step process of the transformations, which consists of (i) base-mediated hydrolytic ring opening of coumarin, (ii) copper-oxygen co-initiated radical decarboxylation, and (iii) copper-catalyzed C-heteroatom cross coupling.

View Article and Find Full Text PDF

It was recognized only recently that the sister norcembranoids scabrolides A and B have notably different carbotricyclic scaffolds. Therefore, our synthesis route leading to scabrolide A could not be extended to its sibling. Rather, a conceptually new approach had to be devised that relied on a challenging intramolecular alkenylation of a ketone to forge the congested central cycloheptene ring at the bridgehead enone site; the required cyclization precursor was attained by a lanthanide-catalyzed Mukaiyama-Michael addition.

View Article and Find Full Text PDF

A reductive amidation of unactivated esters with nitroarenes, a key step in the telescopic synthesis of tetrahydropyrrolo[1,2-]quinoxalinones and tetrahydropyrido[1,2-]quinoxalinones, is reported. The process involves an intermolecular base-mediated SAr reaction, followed by intramolecular reductive amidation employing sodium dithionite. The substrate scope coupled with the demonstration of the synthesis of pharmaceuticals is reported.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!