MODEL-CALCULATIONS OF CHEMICAL INTERACTIONS .6. ORIGIN OF DIASTEREOFACIAL SELECTIVITY IN 1,3-DIPOLAR CYCLOADDITION OF FORMONITRILE OXIDE WITH BICYCLO [2.1.0]PENT-2-ENE AND 2,3-DIOXABICYCLO[2.2.2]OCT-5-ENE
A. Rastelli et al., MODEL-CALCULATIONS OF CHEMICAL INTERACTIONS .6. ORIGIN OF DIASTEREOFACIAL SELECTIVITY IN 1,3-DIPOLAR CYCLOADDITION OF FORMONITRILE OXIDE WITH BICYCLO [2.1.0]PENT-2-ENE AND 2,3-DIOXABICYCLO[2.2.2]OCT-5-ENE, Journal of the Chemical Society. Faraday transactions, 89(21), 1993, pp. 3913-3920
Citations number
25
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
The previous paper in this series, Part 5, gave a novel theoretical an
alysis of the origin of diastereofacial selectivity in 1,3-dipolar cyc
loadditions and discussed the reactions of formonitrile oxide with nor
bornene and cis-3,4-dichlorocyclobutene. The present paper both deepen
s that analysis by defining new quantities related to facial interacti
ons and describes the successful application of the theory to two new
examples, the reactions of formonitrile oxide with bicyclo[2.1.0]pent-
2-ene and 2,3-dioxabicyclo[2.2.2]oct-5-ene, which cover qualitatively
different results from those considered in the earlier work. Total and
facial repulsion, total and facial delocalization and forming-bond de
localization, together with the deformation energy of dipolarophiles a
nd 1,3-dipoles and the stabilization energy of vicinal bond-bond inter
actions, form the conceptual framework for a detailed and coherent acc
ount of the geometry and energy differences between the syn and anti t
ransition structures. Facial repulsions and vicinal interactions invol
ving the forming bonds and the bonds at the allylic positions are the
primary controlling factors of the differential activation energy of s
yn/anti cycloadditions of 1,3-dipoles with double bonds incorporated i
nto rigid cyclic systems.