C10-substituted camphors and fenchones by electrophilic treatment of 2-methylenenorbornan-1-ols: enantiospecificity, scope, and limitations.
Valuable chiral sources of C(10)-substituted camphors and C(10)-substituted fenchones can be straightforwardly obtained by treatment of an appropriate, easily obtainable, camphor- or fenchone-derived 2-methylenenorbornan-1-ol with an electrophilic reagent. The process takes place via a tandem regioselective carbon-carbon double-bond addition/stereocontrolled Wagner-Meerwein rearrangement. A complete study of the enantiospecificity, scope, and limitations of this process, as well as about the role played by the hydroxyl group attached at the C(1) bridgehead position of the starting 2-methylenenorbornan-1-ols, has been realized. The feasibility of the described methodology has been exemplified by the highly efficient enantiospecific preparation of several interesting C(10)-halogen-, C(10)-O-, C(10)-S-, C(10)-Se-, or C(10)-C-substituted camphors and fenchones.
de la Moya Cerero
Santiago
S
Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria, 28040-Madrid, Spain. santmoya@quim.ucm.es
García Martínez
Antonio
A
Teso Vilar
Enrique
E
García Fraile
Amelia
A
Lora Maroto
Beatriz
B
D001892:Camphanes; D002164:Camphor / Q000031:analogs & derivatives* / Q000737:chemistry*; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods*; D006846:Hydrocarbons, Halogenated / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009636:Norbornanes / Q000737:chemistry*; D013237:Stereoisomerism
D001892:Camphanes; D006846:Hydrocarbons, Halogenated; D007202:Indicators and Reagents; D009636:Norbornanes; C027327:fenchone; D002164:Camphor