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Reactivity and Selectivity of Captodative Olefins as Dienes in Hetero ‐Diels – Alder Reactions
Author(s) -
Sanabria Rubén,
Herrera Rafael,
Aguilar Raúl,
GonzálezRomero Carlos,
JiménezVázquez Hugo A.,
Delgado Francisco,
Söderberg Björn C. G.,
Tamariz Joaquín
Publication year - 2008
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.200890194
Subject(s) - chemistry , regioselectivity , reactivity (psychology) , cycloaddition , substituent , selectivity , molecular orbital , ab initio , organic chemistry , medicinal chemistry , computational chemistry , molecule , catalysis , medicine , alternative medicine , pathology
The reactivity and selectivity of the the captodative olefins 1‐acylvinyl benzoates 1a – 1f and 3a as heterodienes in hetero ‐Diels – Alder reactions in the presence of electron‐rich dienophiles is described. Heterodienes 1 undergo regioselective cycloaddition with the alkyl vinyl etherdienophiles 6a , b and 9 to give the corresponding dihydro‐2 H ‐pyrans 7, 8 , and 10 under thermal conditions. The reactivity of these cycloadditions depends, to a large extent, on the electronic demand of the substituent in the aroyloxy group of the heterodiene. Frontier‐molecular‐orbital (FMO; ab initio ) and density‐functional‐theory (DFT) calculations of the ground and transition states account for the reactivity and regioselectivity observed in these processes.