Palladium-Catalyzed Regioselective C–H Alkenylation of Arylacetamides via Distal Weakly Coordinating Primary Amides as Directing Groups

Abstract

Herein we disclose the efficient Pd(II)-catalyzed and regioselective ortho C-H alkenylation of arylacetamide derivatives, viz. weakly coordinating aliphatic primary amides. This protocol utilizes ubiquitous free primary amides as the directing group and circumvents two troublesome steps of installation and removal of an external auxiliary. This strategy directly enables the incorporation of a synthetically versatile olefin in the products in moderate to good yields with regio- and distereoselectivity. The alkenylated acetamides can be easily manipulated and further transformed into a variety of useful derivatives.

Quinone methide dimers lacking labile hydrogen atoms are surprisingly excellent radical-trapping antioxidants

“…Benzylbromide- d 7 ( ref. 41 ) S5 (1.00 g, 5.62 mmol) in ether (1.0 mL) was added over the course of 1 hour to a suspension of activated magnesium (115 mg, 4.82 mmol) in ether (5.0 mL) under a nitrogen atmosphere.…”

Two different facile and efficient approaches for the synthesis of various N-arylacetamides via N-acetylation of arylamines and straightforward one-pot reductive acetylation of nitroarenes promoted by recyclable CuFe2O4 nanoparticles in water

“…their extensive applications in various area such as peptide synthesis, agrochemicals, polymers, functional materials, dyes, fragrances and also existence in pharmaceuticals ( Figure 1) and natural products ( Figure 2) [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25]. Due to the importance of amide compounds, developing simple, practical, environmentally benign, cost-and time-effective manners for their synthesis is very valuable and necessary.…”

Tunable Single and Double γ‐C−H Arylation of Phenylacetamides Directed by o‐Aminophenols

“…Representatively, the 8-aminoquinoline (AQ) directed intramolecular γ-CÀ H amination for the synthesis of pyrrolidin-2-ones has been reported by Chen et al [5] Moreover, Maiti and co-workers have developed the AQ-directed γ-CÀ H alkenylation of phenylacetamides by Pd-catalysis. And extensive efforts in the activation of γ-CÀ H bond have also led to the achievements on the γ-fluorination, [12] γalkeneylation [13] of simple phenylacetamides, as well as the arylation [14] and alkenylation [15] of γ-vinyl CÀ H bond. Complementarily, the alkyl amides with N-AQ structure have been successfully elaborated in γ-site by CÀ H arylation [10] and alkenylation, [11] respectively.…”

“…Complementarily, the alkyl amides with N-AQ structure have been successfully elaborated in γ-site by CÀ H arylation [10] and alkenylation, [11] respectively. And extensive efforts in the activation of γ-CÀ H bond have also led to the achievements on the γ-fluorination, [12] γalkeneylation [13] of simple phenylacetamides, as well as the arylation [14] and alkenylation [15] of γ-vinyl CÀ H bond. Regardless these significant advances, it is also noticeable that most of the aforementioned works employ AQ as the DG, and only a few alternatives are available.…”

“….38 (s, 3 H);13 C NMR (101 MHz, CDCl 3 ): δ 171.69, 148.88, 142.88, 137.66, 137.62, 131.60, 131.03, 130.83, 129.55, 128.98, 128.34, 127.40, 125.45, 122.07, 120.37, 120.02, 41.75, 21.30; ESI-HRMS: Calcd for C 21 H 20 NO 2 [M + H] + : 318.1489; found: 318.1485.…”