4.6 Article

Direct Addition of Grignard Reagents to Aliphatic Carboxylic Acids Enabled by Bulky turbo-Organomagnesium Anilides

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Computational and Experimental Study of Turbo-Organomagnesium Amide Reagents: Cubane Aggregates as Reactive Intermediates in Pummerer Coupling

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Summary: The dynamic equilibria of organomagnesium reagents are studied using DFT calculations and kinetic experiments to investigate the Pummerer coupling between sulfoxides and turbo-organomagnesium amides. Heterometallic open cubane structures are shown to play a key role as reactive intermediates in turbo-organomagnesium amide mixtures through a concerted anion-anion coupling/S-O cleavage step. This research introduces a new reaction pathway and sheds light on the importance of open cubane organometallics in these mixtures.

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