Palladium-Catalyzed C–P Bond-Forming Reactions of Aryl Nonaflates Accelerated by Iodide

Abstract

An iodide-accelerated, palladium-catalyzed C–P bond-forming reaction of aryl nonaflates is described. The protocol was optimized for the synthesis of aryl phosphine oxides and was found to be tolerant of a wide range of aryl nonaflates. The general nature of this transformation was established with coupling to other P(O)H compounds for the synthesis of aryl phosphonates and an aryl phosphinate. The straightforward synthesis of stable, isolable aryl nonaflates, in combination with the rapid C–P bond-forming reaction allows facile preparation of aryl phosphorus target compounds from readily available phenol starting materials. The synthetic utility of this general strategy was demonstrated with the efficient preparation of an organic light-emitting diode (OLED) material and a phosphonophenylalanine mimic.

Synthesis of Phosphorus(V)-Substituted Six-Membered N-Heterocycles: Recent Progress and Challenges

“…Ligand-free microwave-assisted Pd(OAc) 2 -catalyzed phosphorylation of bromopyridines with diphenylphosphine oxide or diethyl phosphite was described by Henyecz et al [ 93 ]. Catalyst Pd(OAc) 2 in the presence of sodium iodide as the promoter was also shown to be an effective catalyst for ligand-free coupling of diphenylphosphine oxide with pyridinium nonaflate [ 94 ]. An example of Pd(PPh 3 ) 4 -catalyzed coupling of 2-bromo-6-pyrrolylpyridine with diethyl phosphite was recently reported by Ti et al [ 95 ].…”

Direct and Rapid Synthesis of Arylphosphines (PIII) by Oxalyl Chloride Promoted Reduction of Inorganic Phosphorus Salts [TBA][H2PO4] with Trichlorosilane and Palladium Catalysis

“…Furthermore, it is speculated that the catalytic pathway for the subsequence synthesis of organic phosphine compounds, triarylphosphines aligned with the well-established coupling reaction with Palladium catalysis (Figures S17 and discussions thereafter.). 49,50,51…”

Micelles Enabled Nickel-Catalyzed P-Arylation of Aromatic Phosphine Oxide in Water Under Mild Conditions

“…Organophosphorus compounds are ubiquitous structural motifs of several bioactive molecules (Figure ), ligands, and polymers. − However, the construction of the aromatic C–P bond via cross-coupling is always challenging because of the inhibitory nature of phosphine precursors, dehalogenation, or deborylation due to the reducing nature of the P–H bond and generally requires high temperature to facilitate reductive elimination. − Therefore, the development of sustainable methodologies for the construction of C–P bonds remains a topic of interest. After the seminal work of Hirao et al on palladium-catalyzed C–P cross-coupling, several approaches for the metal-catalyzed synthesis of organophosphorus compounds have been developed over the years, including the distinct Ni and Cu catalysts or merging them with photoredox and electrocatalysis. − Despite significant development, most of these reactions are conducted using hazardous organic solvents, such as THF, 1,2-dichloroethane (DCE), 1,4-dioxane, and DMF, which has been restricted by the European Commission. , …”