81324-89-2Relevant articles and documents
A Systems Approach to a One-Pot Electrochemical Wittig Olefination Avoiding the Use of Chemical Reductant or Sacrificial Electrode
Chakraborty, Biswarup,Kostenko, Arseni,Menezes, Prashanth W.,Driess, Matthias
supporting information, p. 11829 - 11834 (2020/08/19)
An unprecedented one-pot fully electrochemically driven Wittig olefination reaction system without employing a chemical reductant or sacrificial electrode material to regenerate triphenylphosphine (TPP) from triphenylphosphine oxide (TPPO) and base-free in situ formation of Wittig ylides, is reported. Starting from TPPO, the initial step of the phosphoryl P=O bond activation proceeds through alkylation with RX (R=Me, Et; X=OSO2CF3 (OTf)), affording the corresponding [Ph3POR]+X? salts which undergo efficient electroreduction to TPP in the presence of a substoichiometric amount of the Sc(OTf)3 Lewis acid on a Ag-electrode. Subsequent alkylation of TPP affords Ph3PR+ which enables a facile and efficient electrochemical in situ formation of the corresponding Wittig ylide under base-free condition and their direct use for the olefination of various carbonyl compounds. The mechanism and, in particular, the intriguing role of Sc3+ as mediator in the TPPO electroreduction been uncovered by density functional theory calculations.
Protonation and alkylation of organophosphorus compounds with trifluoromethanesulfonic acid derivatives
Tolstikova,Bel'Skikh,Shainyan
experimental part, p. 474 - 480 (2011/06/23)
Protonation (alkylation) of triphenylphosphine, triethylphosphite, triphenylphosphine oxide, triethylphosphate, hexamethylphosporamide, and dimethylphosphite with trifluoromethanesulfonic acid, its bisimide, and methyl ester was studied and the corresponding 1H, 13C, 19F, 31P NMR spectra were analyzed.
Electroreduction of tetra-coordinate phosphonium derivatives; One-pot transformation of triphenylphosphine oxide into triphenylphosphine
Kuroboshi, Manabu,Yano, Tomotake,Kamenoue, Shogo,Kawakubo, Hiromu,Tanaka, Hideo
experimental part, p. 5825 - 5831 (2011/09/12)
Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al3+, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.
REGENERATION ELECTROCHIMIQUE DE LA TRIPHENYLPHOSPHINE
Lecat, Jean-Luc,Devaud, Marguerite
, p. 5821 - 5822 (2007/10/02)
Triphenylphosphine may be regenerated from triphenylphosphine oxide, by-product of the Wittig reaction, by electrolysis of methylthiotriphenylphosphonium salt prepared with dimethylsulfate by quaternization of the sulfide, obtained from the oxide.
