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A DFT Study of 1,4‐Biradical Intermediates Involved in Stereoselective Paternò–Büchi Reactions
Author(s) -
D'Auria Maurizio,
Racioppi Rocco
Publication year - 2010
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201000045
Subject(s) - stereoselectivity , chemistry , benzaldehyde , enol , computational chemistry , substrate (aquarium) , silylation , coupling reaction , stereochemistry , organic chemistry , catalysis , oceanography , geology
The stereoselectivity of the reaction of silyl enol ethers with benzaldehyde is explained by using DFT calculations, considering the relative stability of the possible stereoisomers of the biradical intermediates and the coupling between the single occupied molecular orbitals (SOMOs) of these intermediates. The same approach can be used to justify the observed endo stereoselectivity in the reaction of 2,3‐dihydrofuran with 2,4,6‐trimethylbenzaldehyde and the exo stereoselectivity in the reaction of the same substrate with 2‐naphthaldehyde.