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Deamination Reactions, 56. Cyclopropane Participation in Norbornyl Cations
Author(s) -
Herrmann Roland,
Kirmse Wolfgang
Publication year - 1995
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.1995199504101
Subject(s) - cyclopropane , chemistry , deamination , 2 norbornyl cation , nucleophile , heptane , bicyclic molecule , medicinal chemistry , ring (chemistry) , nitrous acid , amine gas treating , stereochemistry , organic chemistry , catalysis , enzyme
Nitrous acid deamination of spiro[bicyclo[2.2.1]heptane‐7,1′‐cyclopropan]‐ endo ‐2‐amine ( 13 ) affords 74% of the analogous endo alcohol 24 ‐OH and 26% of the rearranged exo alcohol 25 ‐OH. The exceptional preference for endo attack of the nucleophile is attributed to intervention of the bridged norpinyl cation 21 which is stabilized by the spiroannellated cyclopropane ring. The spiro[bicyclo[2.2.1]heptane‐3,1′‐cyclopropan]‐2‐yl cations 23 arising from Wagner‐Meerwein rearrangement are captured by water to give high exo:endo product ratios.