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Transition State π‐Solvation by Aromatic Rings: An Electronic Contribution to Diels–Alder Reaction Diastereoselectivity
Author(s) -
Evans David A.,
Chapman Kevin T.,
Hung Deborah Tan,
Kawaguchi Alan T.
Publication year - 1987
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198711841
Subject(s) - steric effects , substituent , chemistry , diels–alder reaction , solvation , computational chemistry , aromaticity , stacking , electronic effect , selectivity , character (mathematics) , alkylation , transition state , stereochemistry , photochemistry , organic chemistry , molecule , catalysis , geometry , mathematics
Without making any assumptions regarding the ground‐state conformation , it was possible to determine the electronic contribution of the substituent R to the Diels–Alder selectivity by comparing alkylation and Diels‐Alder reactions involving 1 and 2 . π‐Stacking interactions, which, however, do not exhibit significant charge‐transfer character, are implicated. This was show in part by the observation that, for all substituents that are not capable of π‐stacking for steric or electronic reasons, a linear relation was found to exist between alkylation and Diels‐Alder selectivities.