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            Activation by Borane‐Derived Frustrated Lewis Pairs

Paradies, Jan

doi:10.1002/9783527681020.ch9

Cited by 3 publications

(1 citation statement)

References 108 publications

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“…During these early studies in our group, we realized that a systematically obtained structure–reactivity relationship has so far not been available. − Therefore, we started a systematic investigation into the reactivity of electronically modified Lewis acids and Lewis bases.…”

Section: Initial Studiesmentioning

confidence: 99%

Structure–Reactivity Relationships in Borane-Based FLP-Catalyzed Hydrogenations, Dehydrogenations, and Cycloisomerizations

Paradies

2023

Acc. Chem. Res.

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Conspectus The activation of molecular hydrogen by main-group element catalysts is an extremely important approach to metal-free hydrogenations. These so-called frustrated Lewis pairs advanced within a short period of time to become an alternative to transition metal catalysis. However, deep understanding of the structure–reactivity relationship is far less developed compared to that of transition metal complexes, although it is paramount for advancing frustrated Lewis pair chemistry. In this Account, we provide detailed insight into how Lewis acidity and Lewis basicity correlate to reactivity. The reactivity of frustrated Lewis pairs will be systematically discussed in context with selected reactions. The influence of major electronic modifications of the Lewis pairs is correlated with the ability to activate molecular hydrogen, to channel reaction kinetics and reaction pathways, or to achieve C(sp3)–H activations. First, we will describe how we entered this emerging field of research after quickly realizing that information was lacking on how the reactivity changes with modification of the frustrated Lewis pair. This led us to the development of a qualitative and quantitative structure–reactivity relationship in metal-free imine hydrogenations. The imine hydrogenation was utilized as the model reaction to experimentally determine the activation parameters of the FLP-mediated hydrogen activation for the first time. This kinetic study revealed autoinduced catalytic profiles when Lewis acids weaker than tris(pentafluorophenyl)borane were applied, opening up to study the Lewis base dependency within one system. With this knowledge of the interplay between Lewis acid strength and Lewis basicity, we developed methods for the hydrogenation of densely functionalized nitroolefins, acrylates, and malonates. Here, the reduced Lewis acidity needed to be counterbalanced by a suitable Lewis base to ensure efficient hydrogen activation. The opposite measure was necessary for the hydrogenation of unactivated olefins. For these, comparably less electron-releasing phosphanes were required to generate strong Brønsted acids by hydrogen activation. These systems displayed highly reversible hydrogen activation even at temperatures as low as −60 °C. A systematic study of these systems enabled the development of acceptorless dehydrocouplings of amines with silanes and dehydrogenations of aza-heterocycles by C(sp3)–H activations. Furthermore, the C(sp3)–H and π-activation was utilized to achieve cycloisomerizations by carbon–carbon and carbon–nitrogen bond formations. Lastly, new frustrated Lewis pair systems featuring weak Lewis bases as active components in the hydrogen activation were developed for the reductive deoxygenation of phosphane oxides and carboxylic acid amides.

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Section: Initial Studiesmentioning

confidence: 99%