Regio‐, stereo‐, and site‐selectivities of 1,3‐dipolar Cycloaddition reaction of benzonitrile oxide with unsymmetrically substituted norbornenes and norbornadienes: A computational study

Abstract

In this computational study, density functional theory (DFT) calculations at the M06/6-311G(d,p) level of theory were employed to study the regio-, stereo-, and site-selectivities of 1,3-dipolar cycloadditions of benzonitrile oxide (BNO) with unsymmetrically substituted norbornenes and norbornadienes. The reactions between BNO and unsymmetrically-substituted 2-norbornes and unsymmetrically-substituted 2-norbornadienes proceed with the oxygen of the BNO attacking the more hindered side of the double bond in all cases except when strong EWGs are introduced. For the reaction between BNO and unsymmetrically-substituted 2-norbornadienes, varying degrees of selectivities are observed depending on the substituent, indicating that site-selectivity is largely influenced by nature of substituents. Generally, the regio-isomers in

Searches for bridged bicyclic molecules in space—norbornadiene and its cyano derivatives

“…Literature on the cyano derivatives of NBD is rather scarce compared to their bare chromophore and mostly focused on their photoisomerisation properties 35,36 -of relevance to potential new energy storage solutions-and role in Diels-Alder cycloadditions. 37,38 Spectroscopic information on the gaseous compounds is, to the best of our knowledge, limited to a couple of electronic structure investigations. 39,40 In this paper, we present the pure rotational spectra of NBD and two of its mono-and dicyano-substituted compounds, namely bicyclo[2.2.1]hepta-2,5diene-2-carbonitrile and bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarbonitrile, referred to as CN-NBD and DCN-NBD, respectively.…”

“…Literature on the cyano derivatives of NBD is rather scarce compared to their bare chromophore and mostly focused on their photoisomerisation properties 35,36 —of relevance to potential new energy storage solutions—and role in Diels–Alder cycloadditions. 37,38 Spectroscopic information on the gaseous compounds is, to the best of our knowledge, limited to a couple of electronic structure investigations. 39,40…”