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Journal Article

A Striking Case of Enantioinversion in Gold Catalysis and Its Probable Origins

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Ilg,  Marina K.
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Wolf,  Larry M.
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Mantilli,  Luca
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Farès,  Christophe
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Ilg, M. K., Wolf, L. M., Mantilli, L., Farès, C., Thiel, W., & Fürstner, A. (2015). A Striking Case of Enantioinversion in Gold Catalysis and Its Probable Origins. Chemistry – A European Journal, 21(35), 12279-12284. doi:10.1002/chem.201502160.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0028-E2D1-F
Abstract
The cyclization of the hydroxy-allene 2 to the tetrahydrofuran 3 catalyzed by the gold-phosphoramidite complex 1, after ionization with an appropriate silver salt AgX, is one of the most striking cases of enantioinversion known to date. The major reason why the sense of induction can be switched from (S) to (R) solely by changing either the solvent or the temperature or the nature of the counterion X is likely found in the bias of the organogold intermediates to undergo assisted proto-deauration. Such assistance can be provided by a protic solvent, a reasonably coordinating counterion or even by a second substrate molecule itself; in this case, the reaction free energy profile gains a strong entropic component that can ultimately dictate the stereochemical course.