[3+2] Cycloaddition reaction of 1H-phosphorinium-3-olate and 1-methylphosphorinium-3-olate with methyl acrylate: A DFT study

DFT exploration of [3 + 2] cycloaddition reaction of 1H-phosphorinium-3-olate and 1-methylphosphorinium-3-olate with methyl methacrylate

“…In both gas phase and solvents the more favorable exo TSs are more asynchronous than the endo TSs leading to 6-esters and 7-esters, respectively, with an exception of the 6-esters in solvent for the reaction 1a + MMA where the endo TS is more 21 it is observed that the C1-C5 and C3-C5 forming bonds are shorter whereas the C3-C4 and C1-C4 bonds are longer for the reaction of phosphorinium-3olate with MMA, respectively. Thus, it is also observed that the Dd values increase due to the additional methyl group on the TAC.…”

“… 20 Recently, we studied the regio- and stereoisomeric reaction paths of the 32CA reaction of 1 H -phosphorinium-3-olate and 1-methylphosphorinium-3-olate with MA using the B3LYP/6-31G(d) computational level. 21 It is observed that the formation of the CAs obtained from 32CA reactions of phosphorinium-3-olates is kinetically and thermodynamically more favorable than that of pyridinium-3-olates. 21 …”

“…18 There are limited six-membered heterocycles consisting of phosphorus used as precursors. [19][20][21] The Diels-Alder (DA) reaction of nucleophilic dienes with phosphaalkene was applied by Trauner et al to synthesise phosphinine derivatives. 19 In 2004, substituted l 3phosphabenzene with alkyne was investigated by means of semi-empirical PM3 calculations to nd out the effect of the nature, position and steric hindrance of the substituents on the DA reaction.…”

“…20 Recently, we studied the regio-and stereoisomeric reaction paths of the 32CA reaction of 1Hphosphorinium-3-olate and 1-methylphosphorinium-3-olate with MA using the B3LYP/6-31G(d) computational level. 21 It is observed that the formation of the CAs obtained from 32CA reactions of phosphorinium-3-olates is kinetically and thermodynamically more favorable than that of pyridinium-3olates. 21 In view of our previous study, 21 herein we present a Molecular Electron Density Theory 22 (MEDT) study of 32CA reaction of 1H-phosphorinium-3-olate, 1a, and 1-methylphosphorinium-3olate, 1b, with MMA as shown in Scheme 1.…”

“…21 It is observed that the formation of the CAs obtained from 32CA reactions of phosphorinium-3-olates is kinetically and thermodynamically more favorable than that of pyridinium-3olates. 21 In view of our previous study, 21 herein we present a Molecular Electron Density Theory 22 (MEDT) study of 32CA reaction of 1H-phosphorinium-3-olate, 1a, and 1-methylphosphorinium-3olate, 1b, with MMA as shown in Scheme 1. The methyl group at a carbon of the C-C double bond of MMA acts as steric hindrance in the reaction.…”