Abstract
The rational design based on a deep understanding of the present reaction mechanism is an important, viable approach to discover new organic transformations. β-Hydrogen elimination from palladium complexes is a fundamental reaction in palladium catalysis. Normally, the eliminated β-hydrogen has to be attached to a sp3-carbon. We envision that the hydrogen elimination from sp2-carbon is possible by using thoroughly designed reaction systems, which may offer a new strategy for the preparation of allenes. Here, we describe a palladium-catalyzed cross-coupling of 2,2-diarylvinyl bromides and diazo compounds, where a β-vinylic hydrogen elimination from allylic palladium intermediate is proposed to be the key step. Both aryl diazo carbonyl compounds and N-tosylhydrazones are competent carbene precursors in this reaction. The reaction mechanism is explored by control experiments, KIE studies and DFT calculations.
Highlights
The rational design based on a deep understanding of the present reaction mechanism is an important, viable approach to discover new organic transformations. β-Hydrogen elimination from palladium complexes is a fundamental reaction in palladium catalysis
Palladium catalysis has proved to be a powerful synthetic tool, which is demonstrated by numerous useful transformations and highlighted by the 2010 Nobel Prize in chemistry[1,2,3]
The mechanism involved in those reactions have been extensively explored, efforts to acquire a deep understanding of the current mechanistic hypothesis and apply them to design new transformations have never ceased
Summary
The rational design based on a deep understanding of the present reaction mechanism is an important, viable approach to discover new organic transformations. β-Hydrogen elimination from palladium complexes is a fundamental reaction in palladium catalysis. As an elementary reaction in palladium catalysis, β-hydrogen elimination has been well studied (Fig. 1a)[4,5,6,7].
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