Computational and Experimental Study of Turbo-Organomagnesium Amide Reagents: Cubane Aggregates as Reactive Intermediates in Pummerer Coupling |
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| Authors: | Ferran Planas Stefanie V. Kohlhepp Genping Huang Abraham Mendoza Fahmi Himo |
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| Affiliation: | 1. Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 10691 Stockholm, Sweden;2. Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 P. R. China |
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| Abstract: | The dynamic equilibria of organomagnesium reagents are known to be very complex, and the relative reactivity of their components is poorly understood. Herein, a combination of DFT calculations and kinetic experiments is employed to investigate the detailed reaction mechanism of the Pummerer coupling between sulfoxides and turbo-organomagnesium amides. Among the various aggregates studied, unprecedented heterometallic open cubane structures are demonstrated to yield favorable barriers through a concerted anion-anion coupling/ S−O cleavage step. Beyond a structural curiosity, these results introduce open cubane organometallics as key reactive intermediates in turbo-organomagnesium amide mixtures. |
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| Keywords: | computational chemistry density functional calculations Grignard reaction isotope effects reaction mechanism |
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