626201-15-8Relevant articles and documents
Palladium-Catalyzed C-P Bond-Forming Reactions of Aryl Nonaflates Accelerated by Iodide
McErlain, Holly,Riley, Leanne M.,Sutherland, Andrew
, p. 17036 - 17049 (2021/11/18)
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.
Reactions of Arylsulfonate Electrophiles with NMe4F: Mechanistic Insight, Reactivity, and Scope
Schimler, Sydonie D.,Froese, Robert D. J.,Bland, Douglas C.,Sanford, Melanie S.
, p. 11178 - 11190 (2018/09/12)
This paper describes a detailed study of the deoxyfluorination of aryl fluorosulfonates with tetramethylammonium fluoride (NMe4F) and ultimately identifies other sulfonate electrophiles that participate in this transformation. 19F NMR spectroscopic monitoring of the deoxyfluorination of aryl fluorosulfonates revealed the rapid formation of diaryl sulfates under the reaction conditions. These intermediates can proceed to fluorinated products; however, diaryl sulfate derivatives bearing electron-donating substituents react very slowly with NMe4F. Based on these findings, aryl triflate and aryl nonaflate derivatives were explored, since these cannot react to form diaryl sulfates. Aryl triflates were found to be particularly effective electrophiles for deoxyfluorination with NMe4F, and certain derivatives (i.e., those bearing electron-neutral/donating substituents) afforded higher yields than their aryl fluorosulfonate counterparts. Computational studies implicate a similar mechanism for deoxyfluorination of all the sulfonate electrophiles.
Palladium-Catalyzed Amination of Aryl Nonaflates
Anderson, Kevin W.,Mendez-Perez, Maria,Priego, Julian,Buchwald, Stephen L.
, p. 9563 - 9573 (2007/10/03)
The first detailed study of the palladium-catalyzed amination of aryl nonaflates is reported. Use of ligands 2-4 and 6 allows for the catalytic amination of electron-rich and -neutral aryl nonaflates with both primary and secondary amines. With use of Xantphos 5, the catalytic amination of a variety of functionalized aryl nonaflates resulted in excellent yields of anilines; even 2-carboxymethyl aryl nonaflate is effectively coupled with a primary alkylamine. Moderate yields were obtained when coupling halo-aryl nonaflates with a variety of amines, where in most cases the aryl nonaflate reacted in preference to the aryl halide. Overall, aryl nonaflates are an effective alternative to triflates in palladium-catalyzed C-N bond-forming processes due to their increased stability under the reaction conditions.
