Synthesis and intramolecular reactions of trans-cyclohexyl-1,2-bisacrylate.
Photocycloaddition of dimethyl cyclobut-1-ene-1,2-dicarboxylate (1) with cyclohexene (7) afforded two photoadducts 8 and 9 in 44% and 28% yields, respectively. Spontaneous thermal isomerization of 8 gave (4Z,10Z)-dimethyl cyclodeca-4,10-diene-1,4-dicarboxylate (10), which subsequently isomerized to produce trans-1,2-cyclohexanebis-alpha-acrylic acid dimethyl ester 11. Hydride reduction of the bisacrylate 11 gave the trans-octahydro-1H-inden-2-ols 12a and 15 via a novel, stereoselective, intramolecular reaction. Reaction of the bisacrylate 11 with methyllithium afforded the bis-tertiary alcohol 16. In contrast, lithium dimethylcuprate reacted with the bisacrylate 11 to give the trans-hexahydro-1H-inden-2-one 17 in high yield via a novel, stereoselective, intramolecular reaction.
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122-2585, USA. john.r.williams@temple.edu
John R
JR
Williams
Jianbin
J
Ma
Peter
P
Wepplo
Richard A
RA
Paclin
D000179:Acrylates / Q000138:chemical synthesis* / Q000737:chemistry; D003503:Cyclobutanes / Q000737:chemistry; D003510:Cyclohexanes / Q000138:chemical synthesis* / Q000737:chemistry; D053138:Cyclohexenes; D015394:Molecular Structure; D013059:Spectrum Analysis, Raman; D013237:Stereoisomerism
D000179:Acrylates; D003503:Cyclobutanes; D003510:Cyclohexanes; D053138:Cyclohexenes; C484623:trans-cyclohexyl-1,2-bisacrylate; C052568:cyclohexene