Copper-catalyzed oxidative C‒H, N‒H coupling of azoles and thiophenes

Abstract

C-H, N-H coupling of azole and thiophene derivatives takes place in the presence of a catalytic amount of Cu(OAc) 2 and an additive. The reaction of azoles smoothly occurs with several amines and amides catalyzed by 20 mol% of Cu(OAc) 2-2PPh 3 and 4 equiv. of NaOAc under O 2 or in the presence of Ag 2 CO 3 under N 2. The coupling reaction leads to a facile synthesis of a Nsubstituted analogue of 2,5-diarylthiazole, which shows photoluminescent properties with extended -conjugation. Spectroscopic characteristics of the obtained thiazole derivatives are discussed by measurements of UV-vis absorption and photoluminescent spectra. Under the reaction conditions using Ag 2 CO 3 as an additive and Cu(OAc) 2-2PPh 3 as a catalyst, thiophene derivatives also react with 2-pyrrolidone to undergo C-H, N-H amidation.

Design and Synthesis of a Class of Twin‐Chain Amphiphiles for Self‐Assembled Monolayer‐Based Electrochemical Biosensor Applications

“…1‐(Benzo[ d ]thiazol‐2‐yl)pyrrolidin‐2‐one (9e): Orange solid. Characterization data were identical with the reported data 25…”

Synthesis of N-Aryl and N-Heteroaryl γ-, δ-, and ε-Lactams Using Deprotometalation–Iodination and N-Arylation, and Properties Thereof

“…NMR (CDCl 3 ): δ = 1.92-2.06 (m, 4 H), 2.72 (t, J = 6.8 Hz, 2 H), 4.28 (t, J = 6.2 Hz, 2 H), 7.30 (td, J = 7.6, 1.2 Hz, 1 H), 7.42 (td, J = 7.8, 1.4 Hz, 1 H), 7.82 (t, J = 7.7 Hz, 2 H). NMR (CDCl 3 ): δ = 20.3 (CH 2 ), 22.8 (CH 2 ), 33.2 (CH 2 ), 48.7 (CH 2 ), 121.2 (CH), 121.4 (CH), 124.0 (CH), 126.0 (CH), 133.5 (C), 148.2 (C), 159.4 (C), 170.5 (C).The spectral data are analogous to those described previously 55. Crystal data for 19d: 2(C 13 H 12 NOS), M = 460.59, tetragonal, P-4 2 1 /c, a = 14.2662(9), c = 21.0404(18) Å, V = 4282.2(5) Å 3 , Z = 8, d = 1.429 g cm -3 , μ = 0.277 mm-1 .…”

Copper-Catalyzed Electrophilic Amination of sp2 and sp3 C−H Bonds

“…It is particularly useful because of its high efficacy for substrates, such as benzimidazoles, pyridines, benzothiophenes, and less acidic C−H bonds, which were isolated in poor yields under previous amination conditions. [13][14][15][16][17][18][19][20][21][22][23][24][25][26]64,100 Ar H Ar NR 1 (Table 18). We focused on O-benzoylhydroxylamines as the electrophilic nitrogen source because of their easy availability and previous use in the electrophilic amination of different organometallic reagents.…”

“…[45][46][47][48][49][50][51][52][53][54][55][56][57][58] To our delight, the aminated product One of the important attributes of this new amination approach is its potential to directly access a broad array of heteroaromatic amines, including those inaccessible from other C−H amination methods. [13][14][15][16][17][18][19][20][21][22][23][24][25][26]64,100 Toward this end, we first examined the amination reactions of different azoles using O-benzoylhydroxylamine 3 (Table 19). We We next wanted to expand the heteroarene and arene scope beyond azole compounds (Table 20) (Table 21).…”