1235-21-8Relevant articles and documents
From phosphonium salts to binuclear ortho-palladated phosphorus ylides
Naghipour, Ali,Badpa, Khadijeh,Notash, Behrouz
, p. 349 - 353 (2015)
This current piece of research presents an easy and direct way for the synthesis of binuclear ortho-palladated phosphorus ylide derivatives of acetone and chloroacetone in high yield and high purity by the reaction of the phosphonium salts [CH3COCH2PPh3]Cl (1) and [ClCH2COCH2R]Cl (R = PPh3 (2), R = P(PhMe)3 (3)) with palladium(II) acetate in methanol under mild conditions to afford the dimeric orthopalladated complexes, [Pd(CH3COCHPPh3)(μ-Cl)]2 (4), [Pd(ClCH2COCHPPh3)(μ-Cl)]2 (5) and [Pd(ClCH2COCHP(PhMe)3)(μ-Cl)]2 (6).
Ambident Reactivity of Acetyl- and Formyl-Stabilized Phosphonium Ylides
Byrne, Peter A.,Karaghiosoff, Konstantin,Mayr, Herbert
, p. 11272 - 11281 (2016)
The kinetics and mechanism of the reactions of formyl-stabilized ylide Ph3P=CHCHO (1) and acetyl-stabilized ylide Ph3P=CHCOMe (2) with benzhydrylium ions (Ar2CH+, 3) were investigated by UV-vis and NMR spectroscopy. As ambident nucleophiles, ylides 1 and 2 can react at oxygen as well as at the α-carbon. For some reactions, it was possible to determine the second-order rate constant for O-attack as well as for C-attack and to derive the nucleophile-specific parameters N and sN according to the correlation lg k (20 °C) = sN(E + N) for both nucleophilic sites. Generally, O-attack of benzhydrylium ions is faster than C-attack. However, the initially formed benzhydryloxyvinylphosphonium ions can only be observed by NMR spectroscopy when benzhydryl cations with high Lewis acidity are employed. In other cases, rearrangement to the thermodynamically more stable products arising from C-attack occurs. The results derived from our investigations are employed to rationalize the behavior of ambident nucleophiles 1 and 2 in reactions with carbon-centered electrophiles in general. It is shown that the principle of hard and soft acids and bases (HSAB) and the related Klopman-Salem concept of charge and orbital control lead to incorrect predictions of regioselectivity. We also show that the rate of the Wittig reaction of ylide 2 with aldehyde 14 is significantly faster than the rate of either C- or O-attack calculated using lg k (20 °C) = sN(E + N), thus indicating that the oxaphosphetane is formed by a concerted [2 + 2] cycloaddition.
TREATMENT AND PREVENTION OF HBV DISEASES BY CYCLOSPORINE ANALOGUE MOLECULES MODIFIED AT AMINO ACIDES 1 AND 3
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Page/Page column 29; 30, (2018/06/30)
The present application relates to a method of treating and/or preventing a hepatitis B virus (HBV) disease through inhibiting the interaction of CypA with HBV X protein (HBx) and/or Hepatitis B surface antigen (HBsAg), comprising administering to a subject in need thereof a compound of Formula L.