Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 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.

PubMed Disclaimer

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
See this image and copyright information in PMC

References

    1. Grayson DH. Nat Prod Rep. 2000;17:385–419. - PubMed
    2. Erman WF. In: In Chemistry of the Monoterpenes Part A. Gassman PG, editor. Vol. 11. Marcel Dekker; New York: 1985. pp. 213–249.
    3. Erman WF. In: In Chemistry of the Monoterpenes Part B. Gassman PG, editor. Vol. 11. Marcel Dekker; New York: 1985. pp. 929–1033.
    1. Derfer JM, Traynor SG. The Chemistry of Turpentine. In: Zinkel DF, Russell J, editors. Naval Stores: Production, Chemistry, Utilization. Chapter 8 Pulp Chemicals Association; New York: 1989.
    1. Phillips MA, Savage TJ, Croteau R. Arch Biochem Biophys. 1999;372:197–204. - PubMed
    1. Il’ina IV, Volcho KP, Salakhutdinov NF. Russ J Org Chem. 2008;44:1–23.
    1. Ramachandran PV. Aldrichim Acta. 2002;35:23–35.
    2. Cho BT. Aldrichim Acta. 2002;35:3–16.
    3. Matteson DS. Stereo-directed Synthesis with Organoboranes. Springer-Verlag; Berlin: 1995.

Publication types

MeSH terms