5931-56-6Relevant academic research and scientific papers
Direct and Scalable Electroreduction of Triphenylphosphine Oxide to Triphenylphosphine
Manabe, Shuhei,Sevov, Christo S.,Wong, Curt M.
, p. 3024 - 3031 (2020/03/10)
The direct and scalable electroreduction of triphenylphosphine oxide (TPPO)-the stoichiometric byproduct of some of the most common synthetic organic reactions-to triphenylphosphine (TPP) remains an unmet challenge that would dramatically reduce the cost and waste associated with performing desirable reactions that are mediated by TPP on a large scale. This report details an electrochemical methodology for the single-step reduction of TPPO to TPP using an aluminum anode in combination with a supporting electrolyte that continuously regenerates a Lewis acid from the products of anodic oxidation. The resulting Lewis acid activates TPPO for reduction at mild potentials and promotes P-O over P-C bond cleavage to selectively form TPP over other byproducts. Finally, this robust methodology is applied to (i) the reduction of synthetically useful classes of phosphine oxides, (ii) the one-pot recycling of TPPO generated from a Wittig reaction, and (iii) the gram-scale reduction of TPPO at high concentration (1 M) with continuous product extraction and in flow at high current density.
An efficient heterogeneous cross-coupling of aryl iodides with diphenylphosphine catalyzed by copper (I) immobilized in MCM-41
Fang, Zhiqiang,Cai, Mingzhong,Lin, Yang,Zhao, Hong
, (2018/07/31)
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in toluene at 115?°C in the presence of 10?mol% of phenanthroline-functionalized MCM-41-supported copper (I) complex (Phen-MCM-41-CuI) with Cs2CO3 as base, yielding various unsymmetric triarylphosphines in good to excellent yields. This protocol can tolerate a wide range of functional groups and does not need the use of expensive additives or harsh reaction conditions. This heterogeneous Cu (I) catalyst exhibited the same catalytic activity as homogeneous CuI/Phen system, and could easily be recovered by a simple filtration of the reaction solution and recycled up to seven times without significant loss of activity.
Radical synthesis of trialkyl, triaryl, trisilyl and tristannyl phosphines from P4
Cossairt, Brandi M.,Cummins, Christopher C.
supporting information; experimental part, p. 1533 - 1536 (2010/10/03)
A reaction scheme has been devised according to 3 RX + 3 Ti(iii) + 0.25 P4 → PR3 + 3 XTi(iv), wherein RX = PhBr, CyBr, Me3SiI or Ph3SnCl, with contrasting results in the case of more hindered RX. The scheme accomplishes the direct radical functionalization of white phosphorus without the intermediacy of PCl3.
Radical phosphination of organic halides and alkyl imidazole-1- carbothioates
Sato, Akinori,Yorimitsu, Hideki,Oshima, Koichiro
, p. 4240 - 4241 (2007/10/03)
Taking advantage of a radical-based methodology, mild and chemoselective phosphination reactions of organic halide and alkyl imidazole-1-carbothioates have been developed. The mild reaction conditions allow labile functional groups to survive during the reaction. Copyright
Copper-catalyzed synthesis of unsymmetrical triarylphosphines
Van Allen, Derek,Venkataraman
, p. 4590 - 4593 (2007/10/03)
Various triarylphosphines have been prepared by coupling diphenylphosphine with aryl iodides with catalytic amounts of CuI in the presence of either K2CO3 or CS2CO3, in good yields. This method can tolerate a variety of functional groups and does not require the use of expensive additives, or harsh reaction conditions, and is palladium free.
The Synthesis and Structural Characterization of Mesityldiphenylphosphine, Dimesitylphenylphosphine and Trimesitylphosphine
Blount, John F.,Camp, David,Hart, Robert D.,Healy, Peter C.,Skelton, Brian W.,White, Allan H.
, p. 1631 - 1640 (2007/10/02)
The synthesis and structural characterization of the tertiary phosphines mesityldiphenylphosphine , dimesitylphenylphosphine and a new phase of trimesitylphosphine have been carried out.Crystals of PPh2(mes) are monoclinic, space group P21/c, with a 10.252(10), b 9.847(11), c 17.444(7) Angstroem, β 99.78(6) deg, Z 4; R 0.059 for 2102 "observed" reflections.Crystals of PPh(mes)2 are also monoclinic, space group P21/c, with a 8.964(9), b 22.99(1), c 10.228(4) Angstroem, β 107.98(5) deg, Z 4; R 0.058 for 2350 "observed" reflections.The new phase of P(mes)3 is monoclinic, Cc, a 11.390(5), b 12.034(4), c 17.564(9) Angstroem, β 104.22(4) deg, Z 4 (R 0.060 for 1046 "observed" reflections), in which the molecule is disordered.A full report is given for the phase previously studied (triclinic), P, a 8.191(3), b 16.447(5), c 18.667(6) Angstroem, α 104.82(3), β 97.74(3), γ 100.07(3) deg, Z 4; R 0.065 for 4964 "observed" reflections.The P-C bond distances are similar for the whole series of compounds with an average value of 1.833(1) Angstroem.Introduction of the mesityl groups results in an increase of the C-P-C angles from c. 103 to c. 110 deg with a concomitant flattening of the PC3 pyramid.
Relative Reactivities of Amide, Diphenylphosphide, and Diphenylarsenide Ions toward Aryl Radicals
Alonso, Ruben A.,Bardon, Alicia,Rossi, Roberto A.
, p. 3584 - 3587 (2007/10/02)
Competition experiments have been carried out in liquid ammonia at reflux temperature to determine the relative rate constants for the coupling reactions of amide (NH2-), diphenylphosphide (Ph2P-), and diphenylarsenide (Ph2As-) toward aryl radicals.It is proposed that these nucleophiles react under photostimulation with halo aromatic substrates through an SRN1 mechanism of aromatic substitution.Relative rate constants of NH2- vs.Ph2P- ions toward 2,4,6-trimethylphenyl radicals and Ph2P- vs.Ph2As- ios toward 2-quinolyl radicals have been determined.The results here reported indicate that NH2- (1.00) - (6.4) = Ph2As- (6.4).The fact that there is not a difference in the rate constants of Ph2P- vs.Ph2As- suggests that both nucleophiles react at diffusion-controlled rate.In competition experiments of Ph2P- vs.Ph2As- ions toward phenyl radicals, it was found that Ph2P- (1.00) > Ph2As- (0.44).The decrease of the Ph2As- ion reactivity is attributed to the reversible coupling of this nucleophile with phenyl radicals.
