1,3‐Dipolar Cycloaddition of 4‐Chlorobenzonitrile Oxide with Some Dipolarophiles: Theoretical Analysis of Regioselectivity

Abstract

Reaction of 4‐chlorobenzonitrile oxide (2) which was generated in situ with acrylo nitrile (3), vinyl acetate (4) and allyl bromide (5) as dipolarphile afforded the new cycloadducts 6a, 7a, and 8a compounds, respectively. Reactivity and regiochemistry of these reactions were investigated using activation energy calculations and density functional theory‐based reactivity indexes. The theoretical 13C NMR chemical shifts of the cycloadducts which were obtained by gauge‐invariant atomic orbital method were comparable with the observed values.

Theoretical analysis of the mechanism and regioselectivity of the 1, 3-dipolar cycloaddition of E-3-(dimethylamino)-1-(10H-phenothiazin-2-yl)prop-2-en-1-one with some nitrilimines using DFT and the distortion/interaction model

“…8 Experimentally; it has been found that the cycloaddition reactions of nitrilimines 1a-c with E-3-(dimethylamino)-1-(10H-phenothiazin-2-yl) prop-2-en-1-one 2 give preferentially the cycloadducts 3a, 3b and 3c respectively, shown in Scheme 1. 9 In continuation of our studies on the mechanism and regioselectivity of the1,3-DC reactions, [10][11][12][13][14][15][16][17][18] we became interested in the above mentioned reactions based on activation energy calculations, the distortion/interaction model and DFT-based reactivity indexes.…”