TY - JOUR
T1 - Reactivity and selectivity of captodative olefins as dienes in hetero-Diels-Alder reactions
AU - Sanabria, Rubén
AU - Herrera, Rafael
AU - Aguilar, Raúl
AU - González-Romero, Carlos
AU - Jiménez-Vázquez, Hugo A.
AU - Delgado, Francisco
AU - Söderberg, Björn C.G.
AU - Tamariz, Joaquín
PY - 2008/10
Y1 - 2008/10
N2 - 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-2H-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.
AB - 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-2H-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.
UR - http://www.scopus.com/inward/record.url?scp=55249090172&partnerID=8YFLogxK
U2 - 10.1002/hlca.200890194
DO - 10.1002/hlca.200890194
M3 - Artículo
SN - 0018-019X
VL - 91
SP - 1807
EP - 1827
JO - Helvetica Chimica Acta
JF - Helvetica Chimica Acta
IS - 10
ER -