84127-04-8Relevant articles and documents
Hydrogen/Halogen Exchange of Phosphines for the Rapid Formation of Cyclopolyphosphines
Barrett, Adam N.,Woof, Callum R.,Goult, Christopher A.,Gasperini, Danila,Mahon, Mary F.,Webster, Ruth L.
supporting information, p. 16826 - 16833 (2021/11/04)
The hydrogen/halogen exchange of phosphines has been exploited to establish a truly useable substrate scope and straightforward methodology for the formation of cyclopolyphosphines. Starting from a single dichlorophosphine, a sacrificial proton "donor phosphine"makes the rapid, mild synthesis of cyclopolyphosphines possible: reactions are complete within 10 min at room temperature. Novel (aryl)cyclopentaphosphines (ArP)5 have been formed in good conversion, with the crystal structures presented. The use of catalytic quantities of iron(III) acetylacetonate provides significant improvements in conversion in the context of diphosphine (Ar2P)2 and alkyl-substituted cyclotetra- or cyclopentaphosphine ((AlkylP)n, where n = 4 or 5) formation. Both iron-free and iron-mediated reactions show high levels of selectivity for one specific ring size. Finally, investigations into the reactivity of Fe(acac)3 suggest that the iron species is acting as a sink for the hydrochloric acid byproduct of the reaction.
Copper-catalyzed C–P cross-coupling of secondary phosphines with (hetero)aromatic bromide
Li, Chun-Jing,Lü, Jing,Zhang, Zhi-Xun,Zhou, Kun,Li, Yan,Qi, Guang-Hui
, p. 4547 - 4562 (2018/04/20)
A novel and convenient approach to the synthesis of various tertiary phosphines via a copper-catalyzed cross-coupling of (hetero)aromatic bromide with secondary phosphines has been developed. The reaction employs cheap copper as the catalyst, 2,6-bis(N-methylaminomethyl)pyridine (L4) as a perfect ligand and KOtBu as a base; all reactions are carried out under argon atmosphere. A variety of sterically hindered and/or functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields. Moreover, ten new tertiary phosphines were first reported in this process.
Rapid Metal-Free Formation of Free Phosphines from Phosphine Oxides
Provis-Evans, Cei B.,Emanuelsson, Emma A. C.,Webster, Ruth L.
supporting information, p. 3999 - 4004 (2018/09/21)
A rapid method for the reduction of secondary phosphine oxides under mild conditions has been developed, allowing simple isolation of the corresponding free phosphines. The methodology involves the use of pinacol borane (HBpin) to effect the reduction while circumventing the formation of a phosphine borane adduct, as is usually the case with various other commonly used borane reducing agents such as borane tetrahydrofuran complex (BH3?THF) and borane dimethyl sulfide complex (BH3?SMe2). In addition, this methodology requires only a small excess of reducing agent and therefore compares favourably not just with other borane reductants that do not require a metal co-catalyst, but also with silane and aluminium based reagents. (Figure presented.).