Synthesis of 2-substituted tetraphenylenes via transition-metal-catalyzed derivatization of tetraphenylene

Abstract

SummaryA new strategy for the synthesis of 2-substituted tetraphenylenes through a transition-metal-catalyzed derivatization has been developed. Three types of functionalities, including OAc, X (Cl, Br, I) and carbonyl, were introduced onto tetraphenylene, which allows the easy access to a variety of monosubstituted tetraphenylenes. These reactions could accelerate research on the properties and application of tetraphenylene derivatives.

Ligand‐Free Iron‐Catalyzed Homo‐Coupling of Aryllithium Reagents

“…[7b,18] 1 H NMR (500 MHz, CDCl 3 ) δ = 7.72 (q, J = 8.3 Hz, 8H) ppm. 13 Data was in accordance with that reported in the literature. [7b,17] 4,4'-Bis(trimethylsilyl)-1,1'-biphenyl (2 m).…”

“…Colorless oil. 1 13 C NMR (101 MHz, CD 2 Cl 2 ) δ = 157.6, 131.9, 129.1, 128.4, 120.8, 111.5, 56.1 ppm. Data was in accordance with that reported in the literature.…”

“…[2c,7c] Prepared according to General Procedure 2. Purified by preparative thin-layer chromatography using hexane and ethyl acetate (10 : 1, v/v 13 C NMR (126 MHz, CDCl 3 ) δ = 149.2, 129.9, 126.9, 113.1, 40.8 ppm. Data was in accordance with that reported in the literature.…”

“…178-179°C). [2c,7b] 1 H NMR (500 MHz, CDCl 3 ) δ = 7.49 (d, J = 8.7 Hz, 4H), 6.97 (d, J = 8.7 Hz, 4H), 3.85 (s, 6H) ppm 13. C NMR (126 MHz, CDCl 3 ) δ = 158.7, 133.5, 127.7, 114.1, 55.3 ppm.…”

Acetonitrile as a Building Block and Reactant

“…Protocols for the formation of alkyl aryl ketones have also been developed by C-H activation of an arene using Pd(OAc) 2 /DMSO/TFA followed by carbopalladation of the nitrile (Scheme 50); 253,254 in a reaction with tetraphenylene as the arene, Pd(OAc) 2 /DMSO/TFA was used with CH 2 Cl 2 as an additive. 255 Arylboronic acids also couple with acetonitrile to give methyl ketones. 256 The yield was found to depend on…”