Rearrangement of a mesylate tropane intermediate in nucleophilic substitution reactions. Synthesis of aza-bicyclo[3.2.1]octane and aza-bicyclo[3.2.2]nonane ethers, imides, and amines.
Nucleophilic substitution of 2beta-mesyloxymethyl-N-methyl-3beta-p-tolyl-tropane intermediate with alkoxides, metal imides, or amines was found to lead not only to the expected bicyclo[3.2.1]octane (tropane) ether, imide, and amine derivatives but also to unexpected bicyclo[3.2.2]nonane derivatives. When alkoxides were used as nucleophile, only the rearranged bicyclo[3.2.2]nonane structure was obtained, whereas the use of amines or imides as nucleophile afforded a mixture of the two structures. The bicyclo[3.2.2]nonane structure was assigned by NMR analysis.
Ogier
Lionel
L
Department of Psychiatry, Yale University and VA CT HCS, West Haven, Connecticut, USA.
Turpin
Frédéric
F
Baldwin
Ronald M
RM
Riché
Françoise
F
Law
Ho
H
Innis
Robert B
RB
Tamagnan
Gilles
G
D000473:Alkanes / Q000138:chemical synthesis; D000588:Amines / Q000138:chemical synthesis*; D001372:Aza Compounds / Q000138:chemical synthesis; D001643:Bridged Bicyclo Compounds / Q000737:chemistry; D004987:Ethers / Q000138:chemical synthesis*; D007094:Imides / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008698:Mesylates / Q000737:chemistry; D009795:Octanes / Q000138:chemical synthesis; D014326:Tropanes / Q000138:chemical synthesis* / Q000737:chemistry
D000473:Alkanes; D000588:Amines; D001372:Aza Compounds; D001643:Bridged Bicyclo Compounds; D004987:Ethers; D007094:Imides; D008698:Mesylates; D009795:Octanes; D014326:Tropanes; C017573:nonane