Premium
Pronounced Steric Effects of Substituents in the Nazarov Cyclization of Aryl Dienyl Ketones
Author(s) -
Marcus Andrew P.,
Lee Amy S.,
Davis Rebecca L.,
Tantillo Dean J.,
Sarpong Richmond
Publication year - 2008
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200801542
Subject(s) - reactivity (psychology) , steric effects , allylic rearrangement , aryl , chemistry , diene , medicinal chemistry , substitution (logic) , catalysis , computational chemistry , stereochemistry , organic chemistry , alkyl , computer science , medicine , alternative medicine , natural rubber , pathology , programming language
1,3‐'s a crowd : The facility of the AlCl 3 ‐catalyzed Nazarov cyclization of electron‐rich aryl dienones was found to be dependent upon the substitution of the diene portion (see scheme). For α,γ‐substituted systems, pronounced 1,3‐allylic strain in the reactant is alleviated in the transition state for electrocyclization, leading to enhanced reactivity. DFT calculations support this analysis and have proven to be predictive of reactivity.