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Construction of biaryl monophosphine ligands a Some commercially available biaryl monophosphines. b Palladium-catalyzed carbon-phosphorus bond metathesis. c Rhodium-catalyzed tunable direct arylation of phosphines with aryl bromides.
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The widespread use of phosphine ligand libraries is frequently hampered by the challenges associated with their modular preparation. Here, we report a protocol that appends arenes to arylphosphines to access a series of biaryl monophosphines via rhodium-catalyzed P(III)-directed ortho C–H activation, enabling unprecedented one-fold, two-fold, and t...
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Citations
... The synthesis of molecules with potential applications in optoelectronics [59][60][61] and especially for NLO applications [62][63][64] usually requires complex chemical reactions with high costs for the catalysts and solvents used [65][66][67][68]. This has led to the search for simple reactions with purification processes that guarantee high yields and are economically viable options [62]. ...
... In light of their fundamental importance, many methods of C-P bond formation have been developed [4][5][6]. Among these methods, transition-metal-catalyzed cross-coupling reactions, including the Pd- [7], Cu- [8], Zn- [9], Ni- [10], Mn- [11], Ag- [12], and Rh-catalyzed [13] phosphination reactions of various aryl partners with phosphine reagents, have received great attention [14]. In particular, researchers have focused on developing a mild, efficient, and environmentally benign method of C-P bond formation [15][16][17]. ...
This study investigates the mechanism of metal-free pyridine phosphination with P(OEt)3, PPh3, and PAr2CF3 using density functional theory calculations. The results show that the reaction mechanism and rate-determining step vary depending on the phosphine and additive used. For example, phosphination of pyridine with P(OEt)3 occurs in five stages, and ethyl abstraction is the rate-determining step. Meanwhile, 2-Ph-pyridine phosphination with PPh3 is a four-step reaction with proton abstraction as the rate-limiting step. Energy decomposition analysis of the transition states reveals that steric hindrance in the phosphine molecule plays a key role in the site-selective formation of the phosphonium salt. The mechanism of 2-Ph-pyridine phosphination with PAr2CF3 is similar to that with PPh3, and analyses of the effects of substituents show that electron-withdrawing groups decreased the nucleophilicity of the phosphine, whereas aryl electron-donating groups increased it. Finally, TfO− plays an important role in the C–H fluoroalkylation of pyridine, as it brings weak interactions.
Metal‐catalyzed C−H activation strategies provide an efficient approach for synthesis by minimizing atom, step, and redox economy. Developing milder, greener, and more effective protocols for these strategies is always highly desirable to the scientific community. In this study, the utilization of a single rhodium complex enabled the visible‐light‐induced late‐stage C−H activation of biaryl‐type phosphines with alkynyl bromides, employing inherent phosphorus atoms as directing groups. This chemistry combines P(III)‐directed C−H activation with visible light photocatalysis, under exogenous photosensitizer‐free conditions, offering a unique platform for ligand design and preparation. Furthermore, this study also explores the asymmetric catalysis and coordination chemistry of the resulting P‐alkyne hybrid ligands with specific transition metals. Experimental results and density functional theory calculations demonstrate the mechanistic intricacies of this transformation.
Metal‐catalyzed C−H activation strategies provide an efficient approach for synthesis by minimizing atom, step, and redox economy. Developing milder, greener, and more effective protocols for these strategies is always highly desirable to the scientific community. In this study, the utilization of a single rhodium complex enabled the visible‐light‐induced late‐stage C−H activation of biaryl‐type phosphines with alkynyl bromides, employing inherent phosphorus atoms as directing groups. This chemistry combines P(III)‐directed C−H activation with visible light photocatalysis, under exogenous photosensitizer‐free conditions, offering a unique platform for ligand design and preparation. Furthermore, this study also explores the asymmetric catalysis and coordination chemistry of the resulting P‐alkyne hybrid ligands with specific transition metals. Experimental results and density functional theory calculations demonstrate the mechanistic intricacies of this transformation.
