Palladium/Copper‐Catalyzed Oxidative Arylation of Terminal Alkenes with Aroyl Hydrazides

Abstract

An unprecedented oxidative arylation reaction of terminal alkenes with simple aroyl hydrazides has been developed under aerobic conditions for the stereoselective synthesis of 1,2-disubstituted alkenes. A range of aroyl hydrazides underwent palladium/copper-catalyzed oxidative Mizoroki-Heck reaction with terminal alkenes open to air in a 1:1 mixture of dimethyl sulfoxide and acetonitrile to give structurally diverse 1,2-disubstituted alkenes in moderate to excellent yields with excellent regio- and E-selectivity. The reaction tolerated a wide variety of functional groups, such as alkoxy, hydroxy, amino, fluoro, chloro, bromo, cyano, nitro, ester, amide, imide, phosphine oxide, and sulfone groups, and, moreover, molecular oxygen and dimethyl sulfoxide were demonstrated to serve as terminal oxidants. This study provides a useful method for the stereoselective synthesis of 1,2-disubstituted alkenes through direct transformation of the vinylic CH bonds in terminal alkenes.

The Synthesis and Evaluation of Amidoximes as Cytotoxic Agents on Model Bacterial E. coli Strains

“…The product was purified by column chromatography with silica gel (hexanes/EtOAc) to afford the corresponding product as a colorless solid in 82% yield (168 mg, 0.82 mmol); m.p. 117 13 CNMR data were in accordance with those reported in the literature [13].…”

“…R f 0.28 (hexanes/EtOAc, 7:3). 1 H NMR (400 MHz, CDCl 3 ) δ 7.63-7.53 (m, 2H), 7.44 (d, J = 8.1 Hz, 2H), 7.31-7.17 (m, 5H), 7.10-6.97 (m, 2H), 6.89-6.77 (m, 2H), 6.32 (s, 1H), 6.10 (s, 1H), 4.22 (d, J = 5.7 Hz, 2H), 3.79 (s, 3H), 3.72 (s, 2H); 13…”

Electron Transfer-Induced Coupling of Haloarenes to Styrenes and 1,1-Diphenylethenes Triggered by Diketopiperazines and Potassium tert-Butoxide

“…ν max (neat)/cm −1 3066, 3023, 2965, 2839, 1603, 1595, 1513, 1448, 1249, 1180, 1031, 815; 1 H-NMR (400 MHz, CDCl 3 ) δ 3.84 (3H, s, ArC H 3 ), 6.91 (2H, d, J = 8.8 Hz, Ar H ), 6.98 (1H, d, J = 16.4 Hz, ArC H =CHPh), 7.08 (1H, d, J = 16.4 Hz, ArCH=C H Ph), 7.24–7.28 (1H, m, ArH), 7.36 (2H, t, J = 8.0 Hz, ArH), 7.46–7.51 (4H, m, ArH); 13 C-NMR (100 MHz, CDCl 3 ) δ 55.4 (CH 3 ), 114.2 (CH), 126.4 (CH), 126.7 (CH), 127.3 (CH), 127.8 (CH), 128.3 (CH), 128.8 (CH), 130.2 (C), 137.8 (C), 159.4 (C). Spectral data of this compound were consistent with literature data [ 33 ].…”

Different Schiff Bases—Structure, Importance and Classification

“…Hydrazides also found chemical application inter alia as catalysts of enantioselective reactions in asymmetric aldol reactions [ 83 ], as substrates in regioselective reactions in the preparation of azoheterocycles, such as 1-aryl-1 H -indazoles [ 84 ], or 1,2-disubstituted (in Pd/Cu catalyzed reactions) [ 85 ] and multisubstituted alkenes (Mizoroki–Heck reactions) [ 86 ] and as a sulfenylating reagents in reactions used to obtain indole thioethers [ 87 ]. Hydrazides are also used as protein markers in SSPL (Site-Specific Protein Labeling) methods, in which analyses are performed using spectrometric and electrophoretic (SDS-PAGE) techniques [ 88 ] and as modifiers of magnetic beads in the profiling of surface proteins or mapping N -glycosylation sites in A. nige [ 89 , 90 ].…”