title: Grob fragmentation of norbornyl α-diketones: a route to α-ketoenols and aromatic compounds.
abstract: An efficient acid-catalyzed Grob fragmentation of symmetrical and asymmetrically substituted norbornyl α-diketones to the corresponding six-membered α-ketoenols is reported. The regio- and stereochemical outcome of the Grob fragmentation of C2 mono- and disubstituted α-diketones was investigated. A single regioisomer resulting from a favorable half-chair intermediate was normally observed. A departure from the normal course was noticed for C2 disubstituted α-diketones possessing an exo-methyl and an endo-methoxycarbonyl derivative, giving the opposite regioisomers due to initial formation of the hemiketal. The bromo analogues of the C2 disubstituted α-diketones furnished an unusual byproduct, which appears to have been formed through highly reactive fused four-membered bicyclo[2.2.0]hexane intermediates. A plausible mechanistic proposal involving the gem-dihalo intermediate, which in one case was actually isolated as its BF(2)-complex, is outlined. The fragmentation protocol was applied to various norbornyl substrates including bis-α-diketone derivatives. The methodology was successfully utilized for the synthesis of substituted aromatic compounds.
authors.affiliation: Department of Chemistry, Indian Institute of Technology, Kanpur 208016, India.
authors.forename: Faiz Ahmed
authors.initials: FA
authors.lastname: Khan
authors.forename: Ch Nageswara
authors.initials: ChN
authors.lastname: Rao