TY - JOUR
T1 - Site-Selective Diels-Alder Reactions of 1,4,5,8-Naphthodiquinones with Anthracenes and Successively with Cyclopentadiene
T2 - Elelctronic Effects vs. Steric Effects
AU - Hayakawa, Kenji
AU - Aso, Mariko
AU - Kanematsu, Ken
PY - 1985/6
Y1 - 1985/6
N2 - The cycloaddition reactions of naphthodiquinones with anthracene derivatives have been investigated. While anthracene (4) reacted with naphthodiquinones (1,2, and 13) at the internal double bond to give the internal adducts (6, 7, and 14), the reaction of 9,10-substituted anthracenes (5) took place at the terminal double bond to afford the terminal adducts (8, 9, and 15). The successive reaction of adducts 6 and 7 with cyclopentadiene gave the Diels-Alder adducts 16 and 17, respectively, which were photochemically converted into the cage compounds 18 and 19 in high yields. The reaction of 8 with cyclopentadiene afforded terminal adducts 20, whereas the similar reaction of 9 gave internal adducts 21 which were smoothly converted on irradiation to the cage compounds 22. The site selectivity in these reactions was discussed on the basis of the frontier molecular orbital (FMO) analysis as well as consideration of the steric effects of the substituents.
AB - The cycloaddition reactions of naphthodiquinones with anthracene derivatives have been investigated. While anthracene (4) reacted with naphthodiquinones (1,2, and 13) at the internal double bond to give the internal adducts (6, 7, and 14), the reaction of 9,10-substituted anthracenes (5) took place at the terminal double bond to afford the terminal adducts (8, 9, and 15). The successive reaction of adducts 6 and 7 with cyclopentadiene gave the Diels-Alder adducts 16 and 17, respectively, which were photochemically converted into the cage compounds 18 and 19 in high yields. The reaction of 8 with cyclopentadiene afforded terminal adducts 20, whereas the similar reaction of 9 gave internal adducts 21 which were smoothly converted on irradiation to the cage compounds 22. The site selectivity in these reactions was discussed on the basis of the frontier molecular orbital (FMO) analysis as well as consideration of the steric effects of the substituents.
UR - http://www.scopus.com/inward/record.url?scp=0002628760&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0002628760&partnerID=8YFLogxK
U2 - 10.1021/jo00212a006
DO - 10.1021/jo00212a006
M3 - Article
AN - SCOPUS:0002628760
VL - 50
SP - 2036
EP - 2040
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 12
ER -