Mechanism of the t-BuOM (M = K, Na, Li)/DMEDA-Mediated Direct C–H Arylation of Benzene: A Computational Study

Mahendra Patil

doi:10.1055/s-0040-1707882

Synthesis, Table of Contents

Synthesis 2020; 52(19): 2883-2891
DOI: 10.1055/s-0040-1707882

paper

Mechanism of the t-BuOM (M = K, Na, Li)/DMEDA-Mediated Direct C–H Arylation of Benzene: A Computational Study

Mahendra Patil∗

UM-DAE Centre for Excellence in Basic Sciences, University of Mumbai, Vidyanagari Campus, Kalina, Santacruz (East), Mumbai 400098, India Email: mahendra.patil@cbs.ac.in

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Abstract

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Abstract

Over the past ten years, a combination of organic additive and t-BuOK/t-BuONa has been successfully used for the direct C–H arylation of arenes. Conceptually different from transition-metal-catalyzed cross-coupling reactions, these t-BuOK-mediated reactions have raised significant curiosity among organic chemists. Herein, a systematic computational study of each elementary step of the t-BuOM (M = K, Na, Li)/N ¹,N ²-dimethylethane-1,2-diamine (DMEDA) mediated direct C–H arylation of benzene is detailed. The presented mechanistic proposal relies on the complexation and reaction of t-BuOM with DMEDA (additive), which leads to the formation of different complexes such as SED(M⁺)^…PhI. These complexes mainly involve coordination of the metal ion (from t-BuOM) to the additive and iodobenzene via stabilizing cation–lone pair and cation–π interactions. Such complexation of a metal ion to an additive and iodobenzene not only ensures facile electron transfer to iodobenzene but also provides a lowest energy pathway for the subsequent radical addition and deprotonation step.

Key words

C–H arylation - mechanism - DFT - cross-coupling - potassium tert-butoxide

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References

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Supplementary Material

Supporting Information