Nickel-Catalyzed C(sp³)–H Arylation of Diarylmethane Derivatives with Aryl Fluorides

Abstract

A novel nickel-catalyzed C(sp)-H arylation with nonactivated aryl fluorides is reported. The use of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes) as a ligand was found to be critical to the success of the reaction. This new method enables the synthesis of a wide range of triarylmethane derivatives.

Benzylic Methylene Functionalizations of Diarylmethanes

“…Recently, in 2018, Walsh and group demonstrated another protocol which utilizes non-activated aryl fluorides for C(sp 3 )À H arylation. [60] Their initial attempts utilizing the (NHC)Pd-and (NHC)Ni-based catalyst systems were limited to aryl bromides and chlorides, however, proved ineffective for transformations involving aryl fluorides. Therefore, the authors invented a new catalyst system involving Ni(COD) 2 and IMes to mediate CÀ F bond activation, which promoted the synthesis of triarylmethanes (Scheme 45).…”

“…Recently, in 2018, Walsh and group demonstrated another protocol which utilizes non‐activated aryl fluorides for C(sp 3 )−H arylation . Their initial attempts utilizing the (NHC)Pd‐ and (NHC)Ni‐ based catalyst systems were limited to aryl bromides and chlorides, however, proved ineffective for transformations involving aryl fluorides.…”

Synthesis of 9-biarylfluorenes by one-pot, three-step reactions of N-tosylhydrazones, p-bromobenzeneboronic acid, and arylboronic acids

“…For chromatography, Qingdao Ocean Chemical 200-300 mesh silica gel was employed. 1 H NMR and 13 C NMR spectra were recorded on Bruker Avance III HD 400 MHz spectrometer in CDCl 3 or dimethyl sulfoxide (DMSO)-d 6 solution and the chemical shifts are reported in ppm (δ) relative to the internal standard tetramethylsilane (TMS) (0 ppm). High-resolution mass spectrometry (HRMS) was performed on a Thermo Scientific LTQ or bitrap XL mass spectrometer.…”

“…. 13 Yield: 86%; white solid; m.p. = 139.8-139.5 °C; 1 H NMR (400 MHz, CDCl 3 ): δ 7.81 (d, J = 7.6 Hz, 2H), 7.55 (d, J = 7.1 Hz, 2H), 7.49 (d, J = 8.3 Hz, 2H), 7.41 (q, J = 6.7 Hz, 4H), 7.35 (t, J = 8.2 Hz, 2H), 7.28 (q, J = 7.9, 7.4 Hz, 3H), 7.16 (d, J = 8.2 Hz, 2H), 5.09 (s, 1H); 13 7.47 (dd, J = 7.8, 3.8 Hz, 4H), 7.37 (dd, J = 15.4, 7.5 Hz, 4H), 7.27 (t, J = 7.4 Hz,2H), 7.22 (d, J = 7.9 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 5.08 (s, 1H), 2.66-2.58 (t, J = 7.8 Hz, 2H), 1.64 (p, J = 7.1 Hz, 2H), 1.41-1.28 (m, 4H), 0.90 (t, J = 6.5 Hz, 3H); 13 7.39 (t, J = 7.5 Hz, 2H), 7.37-7.30 (m, 3H), 7.28 (t, J = 6.4 Hz, 2H), 7.14 (dd, J = 7.4, 5.3 Hz, 3H), 7.09 (s, 1H), 6.87 (d, J = 8.2 Hz, 2H), 5.09 (s, 1H), 3.84 (s, 3H); 13…”

“…[4][5][6][7][8][9][10] Recently, 9-biarylfluorenes have been employed in organic chemical reactions and in fluorescent materials applications. [11][12][13][14] However, the preparation of such compounds typically requires complex catalytic systems, non-readily available substrates, and harsh reaction conditions. Thus, it is highly desirable to develop efficient synthetic routes to 9-biarylfluorenes.…”