title: Sequential Diels-Alder reaction/rearrangement sequence: synthesis of functionalized bicyclo[2.2.1]heptane derivatives and revision of their relative configuration.
abstract: A sequential Diels-Alder reaction/rearrangement sequence was developed for the synthesis of diverse functionalized bicyclo[2.2.1]heptanes as novel floral and woody odorants. The outcome of the rearrangement depended on the substitution pattern of the dienes. 2D NMR analysis has established the correct relative configuration of the bicyclo[2.2.1]heptanone, which was originally misassigned. Furthermore, when the initiating DA reaction was catalyzed by a chiral Lewis acid, the bicyclo[2.2.1]heptane derivatives including (+)-herbanone can be obtained in an enantiomeric ratio (er) up to 96.5:3.5.
authors.affiliation: Department of Chemistry, Fudan University , 220 Handan Road, Shanghai 200433, People's Republic of China.
authors.forename: Demin
authors.initials: D
authors.lastname: Liang
authors.forename: Yue
authors.initials: Y
authors.lastname: Zou
authors.forename: Quanrui
authors.initials: Q
authors.lastname: Wang
authors.forename: Andreas
authors.initials: A
authors.lastname: Goeke
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure
chemical_list: D001643:Bridged Bicyclo Compounds; C116378:bicyclo(2.2.1)heptene