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
. 2010 Jan 15;75(2):455-63.
doi: 10.1021/jo9024144.

Origin of stereocontrol in the construction of the 12-oxatricyclo[6.3.1.0(2,7)]dodecane ring system by Prins-pinacol reactions

Larry E Overman  1 , Paul S Tanis
Affiliations

Origin of stereocontrol in the construction of the 12-oxatricyclo[6.3.1.0(2,7)]dodecane ring system by Prins-pinacol reactions

Larry E Overman et al. J Org Chem. .

Abstract

Polycyclic products containing the 12-oxatricyclo[6.3.1.0(2,7)]dodecane moiety having either the trans (8a-e) or cis (9a-e) relative configuration of the oxacyclic bridge and the cis angular substituents are formed stereospecifically by Prins-pinacol cyclizations of unsaturated alpha-dithianyl acetals 14a-e or 15a-e. These results show that the topography (boat or chair) of the Prins cyclization of the sulfur-stabilized oxocarbenium ions generated from acetals 14a-e or 15a-e is controlled by the stereoelectronic influence of the allylic substituents, with steric effects playing a minor role. A complex molecular rearrangement that is terminated by a thio-Prins-pinacol reaction is also identified.

PubMed Disclaimer

Figures

FIGURE 1
FIGURE 1
12-Oxatricyclo[6.3.1.02,7]dodecanes.
SCHEME 1
SCHEME 1
Steric Rationale for Prins–Pinacol Stereoselectivity
SCHEME 2
SCHEME 2
Preparation of Prins–Pinacol Substrates 14a–e and 15a–e
FIGURE 2
FIGURE 2
Conformations of Prins–pinacol products 8 and 9.
SCHEME 3
SCHEME 3
SCHEME 4
SCHEME 4
SCHEME 5
SCHEME 5
Possile Mechanism of Formation of Byproducts 18a–e
See this image and copyright information in PMC

References

    1. For selected recent reviews, see: Tietze LF, Brasche G, Gericke KM. Domino Reactions in Organic Synthesis. Wiley-VCH; Weinheim, Germany: 2006. Nicolaou KC, Edmonds DJ, Bulger PG. Angew. Chem., Int. Ed. 2006;45:7134–7186.Pellissier H. Tetrahedron. 2006;62:1619–1665.Pellissier H. Tetrahedron. 2006;62:2143–2173.M€uller TJJ, editor. Topics in Organometallic Chemistry. Vol. 19. Springer-Verlag; Berlin, Germany: 2006. Metal Catalyzed Cascade Reactions.Chapman CJ, Frost CG. Synthesis. 2007:1–21.Enders D, Grondal C, Huettl MRM. Angew. Chem., Int. Ed. 2007;46:1570–1581.Walji AM, MacMillan DWC. Synlett. 2007:1477–1489.Miyabe H, Takemoto Y. Chem.—Eur. J. 2007;13:7280–7286.Padwa A, Bur SK. Tetrahedron. 2007;63:5341–5378.Kirsch SF. Synthesis. 2008:3183–3204.Yu X, Wang W. Org. Biomol. Chem. 2008;6:2037–2046.

    1. Martinet P, Mousset G, Michel MCR. Acad. Sci. Paris, Ser. C. 1969;268:1303–1306.
    2. Martinet P, Mousset G. Bull. Soc. Chim. Fr. 1970:1071–1076.

    1. For recent reviews, see: Overman LE, Pennington LD. J. Org. Chem. 2003;68:7143–7157.Overman LE. Tetrahedron. 2009;65:6432–6446.

    1. Cohen F, MacMillan DWC, Overman LE, Romero A. Org. Lett. 2001;3:1225–1228. - PubMed
    1. Gahman TC, Overman LE. Tetrahedron. 2002;58:6473–6483.

Publication types