94394-64-6

Upstream product

• 28926-68-3 [(diphenylphosphino)methylene]methyldiphenylphosphorane 
• 104-87-0 4-methyl-benzaldehyde 
• 829-85-6 diphenylphosphane 
• 766-97-2 4-n-methylphenylacetylene 
• 23176-18-3 bis(diphenylphosphino)methane monooxide 

Downstream Products

• 82943-02-0 (E)-(4-methylstyryl)diphenylphosphine sulfide 
• 23901-75-9 (E)-1-(diphenylphosphinyl)-2-(4-methylphenyl)ethene 

Relevant academic research and scientific papers

Synthesis of vinylphosphines and unsymmetric diphosphines: Iron-catalyzed selective hydrophosphination reaction of alkynes and vinylphosphines with secondary phosphines

Iron complex-catalyzed regioselective single hydrophosphination of terminal arylalkynes with secondary phosphines was achieved. Unsymmetric 1,2-bis(phosphino)ethanes with different phosphino groups were obtained by using our catalytic systems. The structu

Mechanistic Investigation of Well-Defined Cobalt Catalyzed Formal E-Selective Hydrophosphination of Alkynes

A formal E-selective hydrophosphination of terminal and internal alkynes catalyzed by a well-defined [Co(PMe3)4] (A) complex is achieved under mild conditions in good-to-excellent yield. The reaction does not require any additives and/or external base for an efficient hydrophosphination reaction. The reaction provided excellent scope and good functional tolerance. Detailed spectroscopic analysis (NMR, EPR, and UV-vis) revealed that the low valent cobalt(0) complex undergoes oxidative addition with diphenylphosphine, followed by hydrometalation with alkyne, and subsequent reductive elimination led to the expected product. The detailed spectroscopic analyses along with the isotopic labeled experiments facilitate to intercept the active intermediates that are involved in the catalytic cycle, which are detailed. It was revealed that the suprafacial (vide infra) delivery of H and phosphorus to π-alkynes in a syn-fashion led to formal E-vinyl phosphine.

Synthesis and molecular structures of divalent bridged bis(guanidinate) europium complexes and their application in intermolecular hydrophosphination of alkenes and alkynes

The reaction of anhydrous EuCl3 with one equiv. of lithium salt of a three-carbon bridged bis(guanidinate) Li2L1 (L1 = [iPr(Me3Si)NC(NiPr)N(CH2)3NC(NiPr)N(SiMe3)iPr]) in THF afforded chloride EuIIIL1Cl(THF)2 (1). The reduction reaction of complex 1 with Na/K alloy in a molar ratio of 1?:?1.2 in THF gave a novel EuII complex supported by an unexpected new bridged bis(guanidinate) ligand L3, [EuIIL3]2 (L3 = [iPr(Me3Si)NC(NiPr)N(CH2)3N(SiMe3)C(NiPr)2]) (2), through the redistribution of one guanidinate in L1 during the reduction. Complex 2 was structurally characterized to be a binuclear complex in which two Eu metals are connected together by two L3 ligands that adopted a μ-η1:η2:η2 coordination mode for one L3 ligand and a μ-η2:η2:η2 mode for the other. Treatment of the in situ formed EuIIIL2Cl(THF)2 (L2 = 1,8-C10H6{NC(NiPr)(NHiPr)}2) by the reaction of EuCl3 with 0.5 equiv. of [Li2L22Li2] in THF with Na/K alloy yielded a novel EuII complex [EuIIL2(THF)]2 (3) in good yield. Complex 3 was characterized by an X-ray crystal structure analysis. Complex 3 features an unusual μ-η1:η2:η2 coordination mode of the bridged bis(guanidinate) ligand onto EuII. Complexes 2 and 3 are efficient pre-catalysts for the intermolecular hydrophosphination of alkenes and alkynes to give exclusively anti-Markovnikov products and mainly anti-addition products for the alkyne reactions. For these transformations, the best performances were observed with complex 2.

Reactivity of lithium diphenylphosphonium diylides towards phosphorus electrophiles: Synthesis of α,β-unsaturated phosphorus compounds

The study of the reactivity of non-stabilized, semi-stabilized and stabilized lithium diphenylphosphonium diylides 1-4 towards Ph2PCl, allowed the synthesis of various α,β-unsaturated phosphines 13-14, via the intermediate formation of the corresponding functionalized monoylides 9-10 and their in situ reaction with carbonyl compounds. In many cases, the reaction is Z-stereoselective and the created double bond can be di- or also trisubstituted. The precise 1H-NMR study of the phosphines 13a-d and the X-ray analysis of 13a (Z isomer) allowed us to assign without ambiguity the stereochemistry of these compounds and to solve a 1H-NMR question. Contrary to reported results in the literature for 13a, we have shown that for the double bond of this phosphine, there is no exception to the general rule 3JHH(trans) > 3JHH(cis). The extension of this reactivity study to other phosphorus electrophiles such as Ph2P(O)Cl, Ph2P(S)Cl and (EtO)2P(O)Cl allowed, as preliminary results, the E-stereoselective synthesis of styrylphosphine oxide and sulfide and diethyl styrylphosphonate.

Preparation of β-Substituted trans-Ethylene Diphenylphosphines and Sulphides by P(O) and P(S)-activated Olefination

Methylene bis-diphenylphosphine monoxide (3c) in toluene reacts regiospecifically and stereoselectively with aldehydes in the presence of potassium tert-butoxide to β-substituted trans-ethylene diphenylphosphines 6, which can be oxidized to the sulphides 2 by sulphur in acetone.These sulphides 2 are to be obtained also directly from methylene bis-diphenylphosphine oxide sulphide 3b and methylene bis-diphenylphosphine disulphide 3d, respectively, under the same olefination conditions.But the yields are smaller and the purification of the raw products is much more difficult, if 3d is used.