21298-89-5

Upstream product

• 6591-07-7 diphenylphosphane sulfide 
• 536-74-3 phenylacetylene 
• 100-52-7 benzaldehyde 
• 127901-19-3 (diphenyl-phosphinothioylmethylene)-methyl-diphenyl-λ⁵-phosphane 
• 1015-37-8 diphenylthiophosphinoyl chloride 
• 829-85-6 diphenylphosphane 
• 1079-66-9 chloro-diphenylphosphine 
• 28926-68-3 [(diphenylphosphino)methylene]methyldiphenylphosphorane 

Relevant academic research and scientific papers

Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes

The hydrophosphination of carbon-carbon multiple bonds has been generally performed under acid, base or metal catalysis in different solvents. Herein, alkyl and alkenyl tertiary phosphines are obtained by the addition of diphenylphosphine to alkenes and alkynes, respectively, in the absence of a solvent and a catalyst. In the presence of elemental sulfur, the corresponding alkyl and alkenyl tertiary phosphine sulfides are synthesized in a three-component process. These simple methods, which meet most of the principles of Green Chemistry, are highly regioselective towards the anti-Markovnikov products and diastereoselective towards the Z alkenyl phosphines. The mechanistic aspects of the reactions are also tackled and the efficiency of the latter is compared with that of the catalytic methods.

Catalyst- and Solvent-Free Stereoselective Addition of Secondary Phosphine Chalcogenides to Alkynes

The addition of secondary phosphine sulfides and selenides to alkynes proceeds readily (80 °C, 5-13 h) without catalysts or solvents to afford regio- and stereoselectively anti-Markovnikov adducts as tertiary alkenylphosphine chalcogenides of Z-configurat

Facile non-catalyzed synthesis of tertiary phosphine sulfides by regioselective addition of secondary phosphine sulfides to alkenes

An atom-economic green synthesis of tertiary phsophine sulfides has been developed based on catalyst- and solvent-free addition of secondary phosphine sulfides to diverse terminal and internal alkenes (hept-1-ene, cyclohexene, styrenes, allyl alcohol, vin

nBuLi-mediated hydrophosphination: A simple route to valuable organophosphorus compounds

A straightforward synthesis of homoallyl- and allylphosphanes has been developed using nBuLi-mediated hydrophosphination of conjugated dienes. In all the cases the phosphorus atom of the reacting phosphane attacked the sterically less demanding side of the diene exclusively. In addition, high regioselectivities towards 1,2- or 1,4-addition products were observed depending on the nature of the dienes. This hydrophosphination reaction was extended to a variety of substrates such as styrene derivatives, alkynes and 1,3,5-cycloheptatriene. The structures of three hydrophosphination products were confirmed by X-ray diffraction studies.

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.

Stereo-controlled synthesis of styrylphosphines and their oxides or sulfides using phosphonium diylides

Lithium dimethyldiphenylphosphonium diylide reacts with electrophiles such as Ph2PCl, Ph2P(O)Cl or Ph2P(S)Cl to give monoylide intermediates allowing by reaction with benzaldehyde the synthesis of the styrylphosphines or the corresponding oxides or sulfides. This efficient one-pot method permits at choice the selective synthesis of each isomer Z or E and corroborates further the isomeric identification of the styrylphosphines.

Dual Radical/Polar Pudovik Reaction: Application Field of New Activation Methods

The Pudovik reaction (addition of organophosphorus compounds containing a labile P-H bond with alkenes and alkynes) can progess via a radical or (and) ionic mechanism. A comparative and systematic study including various reagents and different activation methods (heating, photochemical or ultrasonic irradiation, and dry medium supported reactions) is presented. Photolysis is the most efficient method for the radical processes, but in a few examples, ultrasonic irradiation can be more appropriate since the reaction time is shorter and ultrasound did not induce side-reactions (in particular Z/E isomerization). Dry medium process on basic solid support is the best anionic activation (yield, time, selectivity, purification facilities). Ultrasound, by its mechanical effects, can contribute to increase yield compared to the classical thermal method under these basic conditions. All the activation methods are efficient whatever the unsaturated substrates for the phosphine reactivity, whereas the appropriate activation method is exclusively determined by the nature of the unsaturated system for the thiophosphine (or phosphine oxide) reactivity.