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Theoretical investigation on facial and stereoselectivity in Diels‐Alder cycloadditions of maleic anhydride to dissymmetric cage‐annulated cyclohexa‐1,3‐dienes
Author(s) -
Atalay Abdurrahman,
Abbasoglu Rza
Publication year - 2019
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3893
Subject(s) - chemistry , stereoselectivity , steric effects , maleic anhydride , diene , reagent , computational chemistry , reactivity (psychology) , density functional theory , polar , medicinal chemistry , stereochemistry , organic chemistry , catalysis , alternative medicine , pathology , physics , astronomy , polymer , copolymer , medicine , natural rubber
The facial and stereoselectivity of the polar Diels‐Alder (P‐DA) reaction of dissymmetric cage‐annulated cyclohexa‐1,3‐diene,10,12,13,14‐tetrachloro‐11,11‐dimethoxy‐hexacyclo [7.5.1.0 1,6 .0 6,13 .0 8,12 .0 10,14 ]pentadeca‐2,4‐diene‐7,15‐dione with maleic anhydride, has been theoretically investigated using density functional theory (DFT) method at B3LYP/6‐31G(d) level. Within possible 4 reaction pathways of this P‐DA reaction explored, the anti / endo reactive channel is found to be favored both kinetically and thermodynamically according to calculated results, in compatible with experimental findings. The analysis of DFT‐based global and local reactivity indices of reagents at the ground state enables us to correctly explain the polar nature of these DA reactions' pathways. The presence of steric interactions appeared at exo approaches and nonclassical hydrogen bond interactions seen at endo ones has significant effect on both facial and stereoselectivity of the corresponding DA reaction.