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Issue 7, 2019
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Pushing the limits of concertedness. A waltz of wandering carbocations

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Abstract

Among the array of complex terpene-forming carbocation cyclization/rearrangement reactions, the so-called “triple shift” reactions are among the most unexpected. Such reactions involve the asynchronous combination of three 1,n-shifts into a concerted process, e.g., a 1,2-alkyl shift followed by a 1,3-hydride shift followed by a second 1,2-alkyl shift. This type of reaction so far has been proposed to occur during the biosynthesis of diterpenes and the sidechains of sterols. Here we describe efforts to push the limits of concertedness in this type of carbocation reaction by designing, and characterizing with quantum chemical computations, systems that could couple additional 1,n-shift events to a triple shift leading, in principle to quadruple, pentuple, etc. shifts. While our designs did not lead to clear-cut examples of quadruple, etc. shifts, they did lead to reactions with surprisingly flat energy surfaces where more than five chemical events connect reactants and plausible products. Ab initio molecular dynamics simulations demonstrate that the formal minima on these surfaces interchange on short timescales, both with each other and with additional unexpected structures, allowing us a glimpse into a very complex manifold that allows ready access to great structural diversity.

Graphical abstract: Pushing the limits of concertedness. A waltz of wandering carbocations

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Publication details

The article was received on 10 Aug 2018, accepted on 10 Dec 2018 and first published on 11 Dec 2018


Article type: Edge Article
DOI: 10.1039/C8SC03567A
Citation: Chem. Sci., 2019,10, 2159-2170
  • Open access: Creative Commons BY-NC license
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    Pushing the limits of concertedness. A waltz of wandering carbocations

    M. Castiñeira Reis, C. S. López, O. Nieto Faza and D. J. Tantillo, Chem. Sci., 2019, 10, 2159
    DOI: 10.1039/C8SC03567A

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