2-azapinanes: aza analogues of the enantiomeric pinyl carbocation intermediates in pinene biosynthesis.
The enantiomeric 2-azapinanes, aza analogues of the pinyl carbocation intermediates in pinene biosynthesis, were synthesized from (-)- and (+)-cis-pinonic acids. The individual reactions in the 5-step sequence were Beckmann rearrangement of the pinonic acid oximes, cyclization to the N-acetyl lactams, hydrolysis to the NH-lactams, N-methylations, and LiAlH(4) reductions. The anti stereochemistry of the N-methyl groups in the salts with respect to the gem-dimethyl bridge was established by NOE measurements and by X-ray diffraction analysis.
Department of Chemistry, University of Illinois, Urbana-Champaign, Illinois 61801, USA. faraldosja@Cardiff.ac.uk
Juan A
JA
Faraldos
Benson M
BM
Kariuki
Robert M
RM
Coates
D001372:Aza Compounds / Q000737:chemistry*; D000081008:Bicyclic Monoterpenes; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D008968:Molecular Conformation; D015394:Molecular Structure; D039821:Monoterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D001372:Aza Compounds; D000081008:Bicyclic Monoterpenes; D001643:Bridged Bicyclo Compounds; D039821:Monoterpenes; C010789:beta-pinene; C005451:alpha-pinene
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