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Issue 12, 2016
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Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions

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Abstract

We report a 12-step catalytic enantioselective formal synthesis of malhamensilipin A (3) and diastereoisomeric analogues from (E)-2-undecenal. The convergent synthesis relied upon iterative epoxidation and phosphorus(V)-mediated deoxydichlorination reactions as well a titanium-mediated epoxide-opening to construct the C11–C16 stereohexad. The latter transformation occurred with very high levels of stereoretention regardless of the C13 configuration of the parent epoxide, implicating anchimeric assistance of either the γ- or δ-chlorine atoms, and the formation of chloretanium or chlorolanium ions, respectively. A computational analysis of the chloronium ion intermediates provided support for the involvement of chlorolanium ions, whereas the potential chloretanium ions were found to be less likely intermediates on the basis of their greater carbocationic character.

Graphical abstract: Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions

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Publication details

The article was received on 08 Jul 2016, accepted on 02 Aug 2016 and first published on 02 Aug 2016


Article type: Edge Article
DOI: 10.1039/C6SC03012B
Citation: Chem. Sci., 2016,7, 7040-7049
  • Open access: Creative Commons BY license
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    Synthesis of malhamensilipin A exploiting iterative epoxidation/chlorination: experimental and computational analysis of epoxide-derived chloronium ions

    J. Saska, W. Lewis, R. S. Paton and R. M. Denton, Chem. Sci., 2016, 7, 7040
    DOI: 10.1039/C6SC03012B

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