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Palladium-catalyzed allene synthesis enabled by ?-hydrogen elimination from sp2-carbon.

ABSTRACT: The rational design based on a deep understanding of the present reaction mechanism is an important, viable approach to discover new organic transformations. ?-Hydrogen elimination from palladium complexes is a fundamental reaction in palladium catalysis. Normally, the eliminated ?-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 ?-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.

SUBMITTER: Zhang G 

PROVIDER: S-EPMC7851150 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Palladium-catalyzed allene synthesis enabled by β-hydrogen elimination from sp<sup>2</sup>-carbon.

Zhang Ge G   Song Yi-Kang YK   Zhang Fang F   Xue Ze-Jian ZJ   Li Meng-Yao MY   Zhang Gui-Shan GS   Zhu Bin-Bin BB   Wei Jing J   Li Chunsen C   Feng Chen-Guo CG   Lin Guo-Qiang GQ  

Nature communications 20210201 1

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 sp<sup>3</sup>-carbon. We envision that the hydrogen elimination from sp<sup>2</sup>-carbon is possible by using thoroughly designed reaction systems, which may offer a new strategy fo  ...[more]

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