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

Planas, Ferran; Kohlhepp, Stefanie V.; Huang, Genping; Mendoza, Abraham; Himo, Fahmi

doi:10.1002/chem.202004164

Cited by 4 publications

(2 citation statements)

References 83 publications

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“…For instance, in a recent study of the Pummerer coupling between sulfoxides and turbo-organomagnesium amides (Scheme 4), several structural possibilities, including explicit THF molecules, have been checked. The investigation was able to determine the most stable species that Grignard reagent (isopropylmagnesium chloride) and the magnesium amide ("R-MgX" + DIPAMgCl•LiCL) can form prior to the addition of the sulfoxide [38].…”

Section: Solvent Coordination and Solvent Dynamicsmentioning

confidence: 99%

Beyond Continuum Solvent Models in Computational Homogeneous Catalysis

2021

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In homogeneous catalysis solvent is an inherent part of the catalytic system. As such, it must be considered in the computational modeling. The most common approach to include solvent effects in quantum mechanical calculations is by means of continuum solvent models. When they are properly used, average solvent effects are efficiently captured, mainly those related with solvent polarity. However, neglecting atomistic description of solvent molecules has its limitations, and continuum solvent models all alone cannot be applied to whatever situation. In many cases, inclusion of explicit solvent molecules in the quantum mechanical description of the system is mandatory. The purpose of this article is to highlight through selected examples what are the reasons that urge to go beyond the continuum models to the employment of micro-solvated (cluster-continuum) of fully explicit solvent models, in this way setting the limits of continuum solvent models in computational homogeneous catalysis. These examples showcase that inclusion of solvent molecules in the calculation not only can improve the description of already known mechanisms but can yield new mechanistic views of a reaction. With the aim of systematizing the use of explicit solvent models, after discussing the success and limitations of continuum solvent models, issues related with solvent coordination and solvent dynamics, solvent effects in reactions involving small, charged species, as well as reactions in protic solvents and the role of solvent as reagent itself are successively considered.

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Section: Solvent Coordination and Solvent Dynamicsmentioning

confidence: 99%

Beyond Continuum Solvent Models in Computational Homogeneous Catalysis

2021

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“…We have rationalized these results based on the different aggregation state of these reagents, which we have studied thoroughly in the case of those derived from DIPA ( 12 a ). [15b] …”

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confidence: 99%

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

Colas

Kohlhepp

Mendoza

2022

Chemistry A European J

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The synthesis of ketones through addition of organometallic reagents to aliphatic carboxylic acids is a straightforward strategy that is limited to organolithium reagents. More desirable Grignard reagents can be activated and controlled with a bulky aniline-derived turbo-Hauser base. This operationally simple procedure allows the straightforward preparation of a variety of aliphatic and perfluoroalkyl ketones alike from functionalized alkyl, aryl and heteroaryl Grignard reagents.

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