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. 2013 Dec 2;52(49):12865-8.
doi: 10.1002/anie.201308739. Epub 2013 Nov 19.

Oxidative cyclization reactions: controlling the course of a radical cation-derived reaction with the use of a second nucleophile

Alison Redden  1 , Robert J Perkins, Kevin D Moeller
Affiliations

Oxidative cyclization reactions: controlling the course of a radical cation-derived reaction with the use of a second nucleophile

Alison Redden et al. Angew Chem Int Ed Engl. .

Abstract

Construction of new ring systems: Oxidative cyclizations (see picture; RVC=reticulated vitreous carbon) have been conducted that use two separate intramolecular nucleophiles to trap an enol ether-derived radical cation intermediate. The reactions provide a means for rapidly trapping the radical cation intermediate in a manner that avoids competitive decomposition reactions.

Keywords: anodic cyclizations; electrochemistry; radical ions; reactive intermediates.

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Figures

Figure 1
Figure 1
A potential equilibration of intermediates.
Scheme 1
Scheme 1
Failed anodic cyclization reactions.
Scheme 2
Scheme 2
A plan for avoiding elimination reactions.
Scheme 3
Scheme 3
The initial experiment.
Scheme 4
Scheme 4
Intermolecular trapping.
Scheme 5
Scheme 5
The compatibility of the cyclization with alternative trapping groups.
Scheme 6
Scheme 6
Application to a prior failed cyclization.
See this image and copyright information in PMC

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References

    1. For radical cation-initiated cyclizations derived from chemical oxidations see: Crich D, Ranganathan K, Neelamkavil S, Huang X. J Am Chem Soc. 2003;125:7942.; Crich D, Shirai V, Brebion F, Rumthao S. Tetrahedron. 2006;62:6501.; Crich D, Ranganathan K. J Am Chem Soc. 2005;127:9924.; Crich D, Shirai M, Rumthao S. Org Lett. 2003;5:3767.; Conrad JC, Kong J, Laforteza BN, MacMillan DWC. J Am Chem Soc. 2009;131:11640.; Jui NT, Lee ECY, MacMillan DWC. J Am Chem Soc. 2010;132:10015.; Rendler S, MacMillan DWC. J Am Chem Soc. 2010;132:5027.; Hamilton DS, Nicewicz DA. J Am Chem Soc. 2012;134:18577.; Wilger DA, Gesmundo NJ, Nicewicz DA. Chem Sci. 2013;4:3160.

    1. For general reviews of radical cation-initiated cyclizations derived from electrochemical oxidations see: Moeller KD. Tetrahedron. 2000;56:9527.; Sperry JB, Wright DL. Chem Soc Rev. 2006;35:605.; Yoshida J, Kataoka K, Horcajada R, Nagaki A. Chem Rev. 2009;109:2265.

    1. For a recent review see: Moeller KD. Synlett. 2009;8:1208. For earlier work see reference [2a]. For selected recent examples see: Ashikari Y, Nokami T, Yoshida J. Org Biomol Chem. 2013;11:3322.; Xu HC, Moeller KD. Angew Chem. 2010;122:8176.; Angew Chem Int Ed. 2010;49:8004.; Perkins RJ, Xu HC, Campbell JM, Moeller KD. Beilstein J Org Chem. 2013;9:1630.; Anderson LA, Redden A, Moeller KD. Green Chem. 2011;13:1652.

    1. See for example: Campbell JM, Xu HC, Moeller KD. J Am Chem Soc. 2012;134:18338.; Tang F, Moeller KD. Tetrahedron. 2009;65:10863.; Sun Y, Moeller KD. Tetrahedron Lett. 2002;43:7159.

    1. Tinao-Wooldridge LV, Moeller KD, Hudson CM. J Org Chem. 1994;59:238.

    2. For similar results with a bridged bicyclic system see: Reddy SHK, Chiba K, Sun Y, Moeller KD. Tetrahedron. 2001;57:5183.

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