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. 2011 Mar 4;13(5):836-9.
doi: 10.1021/ol1027893. Epub 2011 Jan 24.

2-azapinanes: aza analogues of the enantiomeric pinyl carbocation intermediates in pinene biosynthesis

Juan A Faraldos  1 , Benson M Kariuki, Robert M Coates
Affiliations

2-azapinanes: aza analogues of the enantiomeric pinyl carbocation intermediates in pinene biosynthesis

Juan A Faraldos et al. Org Lett. .

Abstract

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.

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Figures

Figure 1
Figure 1
Enantiomeric 2-azapinane salts (5·H+ and ent-5·H+), aza analogues of the pinyl carbocation intermediates (C and ent-C) in pinene biosynthesis.
Figure 2
Figure 2
Key NOE correlations observed for [1S, 5R]-2-azapinane trifluoroacetate salt (ent-5·TFA): H1→NH, H1→H6-syn, H6-anti→NMe, NMe→H3-anti, NH→8Me, H3-syn→NH, H3-syn→H4-syn.
Figure 3
Figure 3
ORTEP diagram of [1R, 5S]-2-azapinane hydrochloride (5·HCl) from the X-ray crystal structure determination showing 40% probability with the chloride counter ion omitted.
Figure 4
Figure 4
Structures of pinane-thromboxane A2 and its 2-azapinane analogue
Scheme 1
Scheme 1
Scheme 2
Scheme 2
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