13533-72-7Relevant academic research and scientific papers
Stereoselectivity of 2-methyl-2-norpinyl cations
Herrmann, Roland,Kirmse, Wolfgang
, p. 435 - 438 (2007/10/03)
Optically active (1S)-1-methylbicyclo[2.2.1]heptan-2-one (25) was prepared by starting from (1R)-bicyclo[2.2.1]heptan-2-one (21). Photolysis of the tosylhydrazone 8 of 25 generates, in part, 1-methylbicyclo[2.2.1]heptane-endo-2-diazonium ions (10) from which 1-methylbicyclo[2.2.1]heptan-endo-2-ol (14) and 2-methylbicyclo[3.1.1]heptan-2-ol (16) arise. The ee of both products (42-45%) was found to agree within experimental error. These data point to the bridged 2-methyl-2-norpinyl cation (13) as the most stable structure. Racemization of 13 via the open 2-methyl-2-norpinyl cation (17) as the transition state competes with nucleophilic capture. VCH Verlagsgesellschaft mbH, 1996.
