Synthesis and structure of cyclopropano-annelated homosesquinorbornene derivatives containing pyramidalized double bonds: evidence for the sterical effect of a cyclopropyl group on the degree of C=C double-bond pyramidalization.
[reaction: see text] endo- and exo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl esters have been synthesized, and their Diels-Alder cycloaddition reactions with maleic anhydride, dimethyl acetylenedicarboxylate and singlet oxygen have been investigated. The X-ray analysis of four adducts indicated the pyramidalization of the central double bond. Density functional theory calculations on the isolated products and model compounds showed excellent agreement between the experimental and theoretical determined butterfly angles. Furthermore, it has been shown that a cyclopropyl group fused to [2.2.2] system decreases significantly the degree of the pyramidalization which is attributed to the steric interactions between the cyclopropyl group and ethano bridge of the norbornene systems. Due to the instability of the bicyclic endoperoxides, their X-ray analysis could not be carried out. DFT calculations on model compounds showed increased bending in the case of the product obtained by the addition of singlet oxygen to endo-2,3,4,7-tetrahydro-1H-1,4-methanobenzocycloheptene-7-carboxylic acid ethyl ester.
Department of Chemistry, Atatürk University, 25240 Erzurum, Turkey.
Nurullah
N
Saracoglu
Oktay
O
Talaz
Akín
A
Azizoglu
William H
WH
Watson
Metin
M
Balci
D000983:Antipyrine / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry; D001892:Camphanes / Q000138:chemical synthesis; D002244:Carbon / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003500:Cyclization; D003508:Cycloheptanes / Q000138:chemical synthesis*; D003521:Cyclopropanes / Q000737:chemistry*; D004952:Esters / Q000138:chemical synthesis*; D010100:Oxygen / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry; D012717:Sesquiterpenes / Q000737:chemistry*; D013237:Stereoisomerism
D001643:Bridged Bicyclo Compounds; D001892:Camphanes; D003508:Cycloheptanes; D003521:Cyclopropanes; D004952:Esters; D010545:Peroxides; D012717:Sesquiterpenes; D002244:Carbon; D010100:Oxygen; D000983:Antipyrine