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Deamination Reactions, 58. Stereoselectivity of 2-Methyl-2-norpinyl Cations

✍ Scribed by Herrmann, Roland ;Kirmse, Wolfgang

Publisher
John Wiley and Sons
Year
2006
Tongue
English
Weight
372 KB
Volume
1996
Category
Article
ISSN
0947-3440

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✦ Synopsis

Abstract

Optically active (1__S__)‐1‐methylbicyclo[2.2.1]heptan‐2‐one (25) was prepared by starting from (1__R__)‐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.

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