77382-18-4Relevant articles and documents
Alcohol-based Michaelis-Arbuzov reaction: An efficient and environmentally-benign method for C-P(O) bond formation
Ma, Xiantao,Xu, Qing,Li, Huan,Su, Chenliang,Yu, Lei,Zhang, Xu,Cao, Hongen,Han, Li-Biao
, p. 3408 - 3413 (2018/08/06)
The famous Michaelis-Arbuzov reaction is extensively used both in the laboratory and industry to manufacture tons of widely-used organophosphoryl compounds every year. However, this method and the modified Michaelis-Arbuzov reactions developed recently still have some limitations. We now report a new alcohol-version of the Michaelis-Arbuzov reaction that can provide an efficient and environmentally-benign method to address the problems of the known Michaelis-Arbuzov reactions. That is, a wide range of alcohols can readily react with phosphites, phosphonites, and phosphinites to give all the three kinds of phosphoryl compounds (phosphonates, phosphinates, and phosphine oxides) using an n-Bu4NI-catalyzed efficient C-P(O) bond formation reaction. This general method can also be easily scaled up and used for further synthetic transformations in one pot.
Synthesis and structure of intermediates in copper-catalyzed alkylation of diphenylphosphine
Cain, Matthew F.,Hughes, Russell P.,Glueck, David S.,Golen, James A.,Moore, Curtis E.,Rheingold, Arnold L.
scheme or table, p. 7650 - 7662 (2010/11/19)
Cu(I) catalysts for alkylation of diphenylphosphine were developed. Treatment of [Cu(NCMe)4][PF6] (1) with chelating ligands gave [CuL(NCMe)][PF6] (2; L = MeC(CH2PPh2) 3 (triphos), 3; L = 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (XantPhos)). These complexes catalyzed the alkylation of PHPh2 with PhCH2Br in the presence of the base NaOSiMe3 to yield PPh2CH2Ph (4). The precursors Cu(dtbp)(X) (dtbp =2,9-di-t-butylphenanthroline, X = Cl (5) or OTf (6)), CuCl, and 1 also catalyzed this reaction, but dtbp dissociated from 5 and 6 during catalysis. Both 2 and 3 also catalyzed alkylation of PHPh2 with PhCH 2Cl/NaOSiMe3, but XantPhos dissociation was observed when 3 was used. When CH2Cl2 was used as the solvent for alkylation of PhCH2Cl with precursors 2 or 3, or of PhCH(Me)Br with 2, it was competitively alkylated to yield PPh2CH2Cl (7), which was formed exclusively using 2 in the absence of a benzyl halide. Cu(triphos)-catalyzed alkylation of PhCH(Me)Br gave mostly PPh2CHMePh (8), along with some Ph2P-PPh2 (9), which was also formed in attempted alkylation of dibromoethane with this catalyst. The phosphine complexes [Cu(triphos)(L′)][PF6] (L′ = PH2Ph (10), PH2CH2Fc (Fc = C5H4FeC 5H5, 11), PHPh2 (12), PHEt2 (13), PHCy2 (Cy = cyclo-C6H11, 14), PHMe(Is) (Is = 2,4,6-(i-Pr)3C6H2, 15), PPh2CH 2Ph (16), PPh2CH2Cl (17)), and [Cu(XantPhos)(L′)][PF6] (L′ = PHPh2 (18), PPh2CH2Ph (19)) were prepared by treatment of 2 and 3 with appropriate ligands. Similarly, treatment of dtbp complexes 5 or 6 with PHPh2 gave [Cu(dtbp)(PHPh2)(X)] (X = OTf (20a) or Cl (20b)), and reaction of PPh2CH2Ph (4) with 1 formed [Cu(PPh2CH2Ph)3][PF6] (21). Complexes 2, 3, 11-14, 16, 17, 19, and 21 were structurally characterized by X-ray crystallography. Deprotonation of diphenylphosphine complex 12 in the presence of benzyl bromide gave diphenylbenzylphosphine complex 16, while deprotonation of 12 in CD2Cl2 gave 17 containing a PPh2CD2Cl ligand. Low-temperature deprotonation of the soluble salt 12-[B(ArF)4] (ArF = 3,5-(CF 3)2C6H3) in THF-d8 gave the phosphido complex Cu(triphos)(PPh2) (22). Thermally unstable 22 was characterized by NMR spectroscopy and, in comparison to 12, by density functional theory (DFT) calculations, which showed it contained a polarized Cu-P bond. The ligand substitution step required for catalytic turnover was observed on treatment of 16 or 17 with PHPh2 to yield equilibrium mixtures containing 12 and the tertiary phosphines 4 or 7; equilibrium constants for these reactions were 8(2) and 7(2), favoring complexation of the smaller secondary phosphine in both cases. These observations are consistent with a proposed mechanism for catalytic P-C bond formation involving deprotonation of the cationic diphenylphosphine complex [Cu(triphos)(PHPh2)][PF 6] (12) by NaOSiMe3 to yield the phosphido complex Cu(triphos)(PPh2) (22). Nucleophilic attack on the substrate (benzyl halide or CH2Cl2) then yields the tertiary phosphine complex [Cu(triphos)(PPh2CH2X)][PF6] (X = Ph (16) or Cl (17)), and ligand substitution with PHPh2 regenerates 12.
Studies on the efficient generation of phosphorus-carbon bonds via a rearrangement of PIII esters catalysed by trimethylhalosilanes
Dabkowski, Wojciech,Ozarek, Alfred,Olejniczak, Sebastian,Cypryk, Marek,Chojnowski, Julian,Michalski, Jan
experimental part, p. 1747 - 1756 (2009/09/25)
Halotrimethylsilanes Me3SiX (X = Br, I) catalyse rearrangements of tricoordinate phosphorus esters R′R″P-OR into the corresponding phosphoryl systems R′R″P(O)R. This provides a simple and efficient route to a variety of structures containing phosphorus-carbon bonds, under mild conditions and with good yields. The reaction mechanism was investigated in detail by 31P NMR spectroscopy and independent synthesis of the reaction intermediates. It has been demonstrated that the primary products of this catalytic reaction are halogeno PIII structures R′R″PX and silyl ethers ROSiMe3 and that they subsequently react to give the corresponding phosphorus silyl esters - Me 3SiOPR′R″-and alkyl halides RX. At higher temperatures these intermediates then react to form R′R″P(P)R compounds. This paper also features the surprising observation that when esters Ph 2POR and halotrimethylsilanes Me3SiX (X = Br, I) are used in 2:1 ratio, phosphonium salts Ph2R2P+X - and trimethylsilyl diphenylphosphinate - Ph2P(O) OSiMe3 - are formed as the major products. Experimental evidence indicates that the mechanisms of both reactions are fundamentally different from that of the Michaelis-Arbuzov reaction. Me3SiCl is not reactive and this paper explains why.
The synthesis of alkenes via epi-phosphonium species: 2. A phosphorus Ramberg-Backlund reaction
Lawrence, Nicholas J.,Muhammad, Faiz
, p. 15361 - 15370 (2007/10/03)
Stilbene may be synthesised with Z-selectivity from (α- bromobenzyl)benzyldiphenylphosphonium bromide by the action of amine bases. A series of stilbenes was synthesised by the action of N-bromosuccinimide and 2,2,6,6-tetramethylpiperidine directly upon dibenzyldiphenylphosphonium salts. The reaction, essentially a phosphonium analogue of the Ramberg- Backlund displays cis selectivity. The dibenzyldiphenylphosphonium salts were prepared by the one pot polymethylhydrosiloxane/titanium(IV) isopropoxide mediated reduction/alkylation of benzyldiphenylphosphine oxides.
Titanium (IV) catalysis in the reduction of phosphine oxides
Coumbe, Tristan,Lawrence, Nicholas J.,Muhammad, Faiz
, p. 625 - 628 (2007/10/02)
Phosphine oxides can be reduced by triethoxysilane, or more conveniently polymethylhydrosiloxane, and catalytic titanium (IV) isopropoxide and provides a system for the efficient one-pot generation of phosphonium salts; the reduction occurs with retention of configuration at phosphorus.
Ramberg Baecklund type reactions of phosphonium salts
Lawrence, Nicholas J.,Muhammad, Faiz
, p. 5903 - 5906 (2007/10/02)
Alkenes may be synthesised from (α-bromobenzyl)benzyldiphenylphosphonium salts by the action of amine bases. A series of stilbenes was synthesised by the action of N-bromosuccinimide and 2,2,6,6-tetramethylpiperidine directly upon dibenzyldiphenylphosphonium salts. The reaction, essentially a phosphonium analogue of the Ramberg Baecklund displays a similar level of cis selectivity as that shown by the parent sulfone.
Synthesis of Diphenyldialkylphosphonium Salts
Cristau, Henri-Jean,Ribeill, Yves
, p. 911 - 912 (2007/10/02)
A general method for synthesis of the title compounds by a one-pot reaction is described.It consists in the double alkylation of lithium diphenylphosphide, obtained by the reaction of triphenylphosphine, lithium and tert-butyl chloride.This procedure can also be used for α-functional alkylating agents.
