Carbene chemistry : I. Stereochemical integrity at Cα in ketone tosylhydrazones : II. Hydrogen migration in 2-carbena-6, 6-dimethylnorbornane Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/6682x8222

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  • The tosylhydrazones of exo-3-deuteriocamphor and 2- deuterio-2,4-dimethy1-3-pentanone were treated with Nbromosuccinimide (NBS) and pyruvic acid to regenerate the parent ketones. The ketones from the pyruvic acid cleavage show a significant loss of deuterium. The ketones from the NBS cleavage show no loss of deuterium, indicating that stereochemical integrity at. C[subscript α] is maintained during the NBS cleavage. The tosylhydrazones and corresponding lithium salts of exo and endo-3-deuterio-6,6-dimethylnorbornan-2-one are found to maintain their stereochemical integrity at C[subscript α]. Thermal and photolytic decomposition of the lithium salts reveals a 3,2 hydride migration preference of 19:1 in favor of the exo hydrogen. Torsional interactions in the hydride migration transition state of a classical singlet carbene are suggested as an explanation for the observed stereoselectivity.
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