A Versatile and Efficient Ligand for Copper‐Catalyzed Formation of CN, CO, and PC Bonds: Pyrrolidine‐2‐Phosphonic Acid Phenyl Monoester

Abstract

A new and readily available bidentate ligand, namely, pyrrolidine-2-phosphonic acid phenyl monoester (PPAPM), has been developed for the copper-catalyzed formation of C-N, C-O, and P-C bonds, and various N-, O-, and P-arylation products were synthesized in good to excellent yields by using the CuI/PPAPM catalyst system. Addition of the PPAPM ligand greatly increases the reactivity of the copper catalyst, and the resulting versatile and efficient catalyst system is of widespread and practical application in cross-coupling reactions.

Recent Advances in H-Phosphonate Chemistry. Part 2. Synthesis of C-Phosphonate Derivatives

“…The first catalytic procedure for Cu(I)-mediated coupling of aryl halides with H-phosphonate diesters, based on the Ullmann-type of chemistry, was described in 2003 by Buchwald [129,130] et al [132]. Since then, the number of applications of copper as a catalyst has steadily increased [133][134][135].…”

Carbene adduct of cyclopalladated ferrocenylimine as an efficient catalyst for the amination of aryl chlorides

“…N-(2-Methoxyphenyl)aniline (Table 4, entry 4) [23]. Pale yellow oil; 1 H NMR: d 7.31-7.24 (3H, m), 7.14-7.12 (2H, m), 6.94-6.91 (1H, m), 6.89-6.83 (3H, m), 6.14 (1H, s), 3.86 (3H, s).…”

Mixed-ligand complexes of copper(I) with Schiff base and triphenylphosphine: Effective catalysts for the amination of aryl halide

“…Although the Pd-catalyzed amination of aryl halide has recently become the most important method for laboratory scale synthesis of arylamines; copper stands out as a convenient alternative to palladium catalysts, because copper salts are often cheap and environmentally benign. Many ligand systems such as amino acid [10], diamines [11], di-imines [12], aminoarenethiolate [13], phosphine [14,15] and other nitrogen, oxygen containing ligands [16][17][18][19] together with copper(I) reagents have been applied for the production of arylamines under mild condition.…”