TY - JOUR
T1 - Highly Selective Diels-Alder Cycloadditions of Captodative Dienophiles 1-Acetylvinyl Arenecarboxylates to Unsymmetrically Substituted Butadienes
AU - Reves, Alicia
AU - Aguilar, Raul
AU - Munoz, Alfredo H.
AU - Tamariz, Joaquin
AU - Zwick, Jean Christophe
AU - Rubio, Manuel
AU - Escobar, Jose Luis
AU - Soriano, Manuel
AU - Toscano, Ruben
PY - 1990
Y1 - 1990
N2 - Thermal Diels-Alder cycloadditions of captodative olefins 1-acetylvinyl arenecarboxylates, CH2—C(COC-H3)OCOAr, la (Ar = C6H4pNO2), lb (Ar = a-naphthyl), and lc (Ar = β-naphthyl), with isoprene (2) were shown to be regioselective. This regioselectivity was greatly improved by using Lewis acids catalysis (ZnCl2, BF3.Et2O), the para adduct being the main isomer. The addition of dienophile la to 1-substituted dienes 3, 4, and 6 and 1.3- disubstituted butadiene 5 was highly regioselective too, and the ortho isomer was the only observed adduct. Stereoselectivity of these reactions was examined, and it was determined for all of these dienes, including the 1.4- diacetoxybutadiene (7), that the endo stereoisomer was obtained in a high proportion (>80%). The structure of major adducts 8a, 18a, 20a, 22a, 26a, and 29a was established by lH and 13C NMR spectroscopy. Regioselectivity of these cycloadditions has been rationalized in terms of the FMO theory by MO calculations of dienophiles 1, using MINDO/3 and ab initio methods. It is suggested that secondary orbital interactions might be responsible for the observed endo selectivity.
AB - Thermal Diels-Alder cycloadditions of captodative olefins 1-acetylvinyl arenecarboxylates, CH2—C(COC-H3)OCOAr, la (Ar = C6H4pNO2), lb (Ar = a-naphthyl), and lc (Ar = β-naphthyl), with isoprene (2) were shown to be regioselective. This regioselectivity was greatly improved by using Lewis acids catalysis (ZnCl2, BF3.Et2O), the para adduct being the main isomer. The addition of dienophile la to 1-substituted dienes 3, 4, and 6 and 1.3- disubstituted butadiene 5 was highly regioselective too, and the ortho isomer was the only observed adduct. Stereoselectivity of these reactions was examined, and it was determined for all of these dienes, including the 1.4- diacetoxybutadiene (7), that the endo stereoisomer was obtained in a high proportion (>80%). The structure of major adducts 8a, 18a, 20a, 22a, 26a, and 29a was established by lH and 13C NMR spectroscopy. Regioselectivity of these cycloadditions has been rationalized in terms of the FMO theory by MO calculations of dienophiles 1, using MINDO/3 and ab initio methods. It is suggested that secondary orbital interactions might be responsible for the observed endo selectivity.
UR - http://www.scopus.com/inward/record.url?scp=0025343348&partnerID=8YFLogxK
U2 - 10.1021/jo00290a039
DO - 10.1021/jo00290a039
M3 - Artículo
SN - 0022-3263
VL - 55
SP - 1024
EP - 1034
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 3
ER -