02085nas a2200253   4500008004100000022001400041245013600055210006900191260000900260300001400269490000700283520119800290653001401488653001501502653002001517653001901537653003601556100002201592700001901614700002501633700001701658700002401675856013201699       2017                        eng d  a0947-653900aElectronic control on linear versus branched alkylation of 2-/3-aroylbenzofurans with acrylates: combined DFT and synthetic studies0 aElectronic control on linear versus branched alkylation of 23aro  cJUN   a7570-75810 v233 a<p>Investigations on the factors that govern unusual branched alkylation of 2-aroylbenzofurans with acrylates by Ru-catalyzed carbonyl-directed C-H activation has been carried out by calculating the kinetics associated with the two key steps-the coordination of the acrylate with the intermediate ruthenacycle and the subsequent migratory insertion reaction-studied with the help of DFT calculations. Eight possible orientations for each mode of alkylation have been considered for the calculations. From these calculations, it has been understood that there is a synergistic operation of the steric and electronic effects favoring the branched alkylation. Further DFT investigations on the alkylation of the isomeric 3-aroylbenzofurans indicated a preference for the linear alkylation and this has been verified experimentally. Overall, the observed/calculated complementary selectivity in the alkylation of 2-/3-aroylbenzofurans with acrylates reveals that the substrate-dependent charge distribution of the Ru-C bond in the intermediate ruthenacycle is an important determining factor and thus the current work opens up a new domain of substrate design for controlling regioselectivity.</p>10aacrylates10aAlkylation10aaroylbenzofuran10aC-H activation10aDensity functional calculations1 aSrinivas, Kolluru1 aDangat, Yuvraj1 aKommagalla, Yadagiri1 aVanka, Kumar1 aRamana, Chepuri, V.  uhttps://library.ncl.res.in/content/electronic-control-linear-versus-branched-alkylation-2-3-aroylbenzofurans-acrylates-combined