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.
Ru(II)-Catalyzed Amination of Aryl Fluorides via η6-Coordination
Kang, Qi-Kai,Li, Yuntong,Lin, Yunzhi,Shi, Hang
supporting information, p. 3706 - 3711 (2020/03/11)
We developed a Ru/hemilabile-ligand-catalyzed nucleophilic aromatic substitution (SNAr) of aryl fluorides as the limiting reagents. Significant ligand enhancement was demonstrated by the engagement of both electron-rich and neutral arenes in the SNAr amination without using excess arenes. Preliminary mechanistic studies revealed that the nucleophilic substitution proceeds on a η6-complex of the Ru catalyst and the substrate, and the hemilabile ligand facilitates dissociation of products from the metal center.
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.
Tailored Cobalt-Catalysts for Reductive Alkylation of Anilines with Carboxylic Acids under Mild Conditions
Liu, Weiping,Sahoo, Basudev,Spannenberg, Anke,Junge, Kathrin,Beller, Matthias
supporting information, p. 11673 - 11677 (2018/09/10)
The first cobalt-catalyzed hydrogenative N-methylation and alkylation of amines with readily available carboxylic acid feedstocks as alkylating agents and H2 as ideal reductant is described. Combination of tailor-made triphos ligands with cobalt(II) tetrafluoroborate significantly improved the efficiency, thus promoting the reaction under milder conditions. This novel protocol allows for a broad substrate scope with good functional group tolerance, even in the presence of reducible alkenes, esters, and amides.
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.).
Metal-Free Reduction of Phosphine Oxides, Sulfoxides, and N-Oxides with Hydrosilanes using a Borinic Acid Precatalyst
Chardon, Aurélien,Maubert, Orianne,Rouden, Jacques,Blanchet, Jér?me
, p. 4460 - 4464 (2017/11/22)
The general reduction of phosphine oxides, sulfoxides, and amine N-oxides was achieved by combining bis(2-chlorophenyl)borinic acid with phenylsilane. The reaction was shown to tolerate a wide range of substrates and could be performed under mild conditions, with only 2.5 mol % of the easily synthesized catalyst. Mechanistic investigations pointed to a key borohydride as the real catalyst and at bis(2-chlorophenyl)borinic acid as a precatalyst.
Facile, Catalytic Dehydrocoupling of Phosphines Using β-Diketiminate Iron(II) Complexes
King, Andrew K.,Buchard, Antoine,Mahon, Mary F.,Webster, Ruth L.
supporting information, p. 15960 - 15963 (2015/11/03)
Catalytic dehydrocoupling of primary and secondary phosphines has been achieved for the first time using an iron pre-catalyst. The reaction proceeds under mild reaction conditions and is successful with a range of diarylphosphines. A proton acceptor is not needed for the transformation to take place, but addition of 1-hexene does allow for turnover at 50°C. The catalytic system developed also facilitates the dehydrocoupling of phenylphosphane and dicyclohexylphosphane. A change in solvent switches off dehydrocoupling to allow hydrophosphination of alkenes.
Selective dehydrocoupling of phosphines by lithium chloride carbenoids
Molitor, Sebastian,Becker, Julia,Gessner, Viktoria H.
, p. 15517 - 15520 (2014/12/12)
The development of a simple, transition-metal-free approach for the formation of phosphorus-phosphorus bonds through dehydrocoupling of phosphines is presented. The reaction is mediated by electronically stabilized lithium chloride carbenoids and affords a variety of different diphosphines under mild reaction conditions. The developed protocol is simple and highly efficient and allows the isolation of novel functionalized diphosphines in high yields.
Catalyst-free alcoholysis of phosphane-boranes: a smooth, cheap, and efficient deprotection procedure
Van Overschelde, Michel,Vervecken, Elias,Modha, Sachin G.,Cogen, Simon,Van der Eycken, Erik,Van der Eycken, Johan
experimental part, p. 6410 - 6415 (2009/12/09)
Catalyst-free alcoholytic deprotection of borane-protected phosphorus compounds offers a smooth, efficient, and clean alternative to existing deprotection methods. In this paper we report our results on the general applicability of deprotecting phosphane-
