104629-24-5Relevant academic research and scientific papers
Preparation of 2-phospholene oxides by the isomerization of 3-phospholene oxides
Bagi, Péter,Herbay, Réka,Keglevich, Gy?rgy,Mucsi, Zoltán,Péczka, Nikolett,Timári, István
, p. 818 - 832 (2020/05/14)
A series of 1-substituted-3-methyl-2-phospholene oxides was prepared from the corresponding 3-phospholene oxides by double bond rearrangement. The 2-phospholene oxides could be obtained by heating the 3-phospholene oxides in methanesulfonic acid, or via the formation of cyclic chlorophosphonium salts. Whereas mixtures of the 2- and 3-phospholene oxides formed, when the isomerization of 3-phospholene oxides was attempted under thermal conditions, or in the presence of a base. The mechanisms of the various double bond migration pathways were elucidated by quantum chemical calculations.
Dynamic kinetic resolution of 1-substituted-3-methyl-3-phospholene oxides via the formation of diastereomeric alkoxyphospholenium salts
Bagi, Péter,Herbay, Réka,ábrányi-Balogh, Péter,Mátrav?lgyi, Béla,Fogassy, Elemér,Keglevich, Gy?rgy
, p. 5850 - 5857 (2018/08/29)
A dynamic kinetic resolution method based on the formation of covalent diastereomeric intermediates was elaborated for the preparation of enantiomerically enriched 1-substituted-3-methyl-3-phospholene oxides. The 3-phospholene oxides were first converted to the corresponding chloro-3-phospholenium chlorides. The dynamic interconversion between the enantiomers of the chlorophospholenium salts was verified experimentally, as it is the key step for a dynamic resolution. The cyclic chlorophospholenium salts were reacted with a chiral auxiliary bearing a hydroxy function to form the corresponding diastereomeric alkoxyphospholenium salts in unequal amounts. The diastereomeric species then rearranged into the corresponding optically active 3-phospholene oxides upon heating. After a screening of chiral auxiliaries and the optimization of the reaction conditions, several scalemic 1-aryl- or 1-alkyl-3-methyl-3-phospholene oxides were prepared in excellent yields and with ee-s up to 35%. The key steps of this resolution were investigated by quantum chemical calculations to get some insights into the factors responsible for the stereoselection.
REACTION OF PHOSPHOLES WITH ACIDS; PROTON SHIFTS IN 1H-λ5-PHOSPHOLES
Quin, Louis D.,Belmont, Stephen E.,Mathey, Francois,Charrier, Claude
, p. 629 - 634 (2007/10/02)
Addition to phospholes of gaseous HCl at -90 deg C or of an excess of trifluoromethanesulphonic acid at -70 deg C, results in P-protonation.The triflate solutions are stable up to room temperature, but the 1H-phospholium chlorides form PV adducts at -70 deg C, which rapidly rearrange by a sigmatropic H-shift.The observed product is a 1-chloro-2,5-dihydrophospholium chloride.Addition of a chloride ion source to the triflates produces the same result.Unprotonated 3,4-dimethyl-1-phenyl phosphole was found to react at a double bond of its 1H-phospholium ion, forming a crystalline 1,3'-biphospholium dimer.
