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Divergent Reactivity in Pd-Catalyzed [3,3]-Sigmatropic Rearrangement of Allyloxy- and Propargyloxyindoles Revealed by Computation and Experiment.

ABSTRACT: Detailed computational (DFT) studies of the palladium(II)-catalyzed Claisen rearrangement of 2-allyloxy- and propargyloxyindoles revealed an unexpected divergent mode of reactivity. Subsequent experimental kinetic isotope effects are in accord with the mechanism derived from the computations. The computational results led to the development of Pd(II)-catalyzed [3,3]-sigmatropic rearrangement of 3-aryl substituted 2-propargylindoles.

SUBMITTER: Gutierrez O

PROVIDER: S-EPMC6201310 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

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Divergent Reactivity in Pd-Catalyzed [3,3]-Sigmatropic Rearrangement of Allyloxy- and Propargyloxyindoles Revealed by Computation and Experiment.

Gutierrez Osvaldo O Hendrick Charles E CE Kozlowski Marisa C MC

Organic letters 20181008 20

Detailed computational (DFT) studies of the palladium(II)-catalyzed Claisen rearrangement of 2-allyloxy- and propargyloxyindoles revealed an unexpected divergent mode of reactivity. Subsequent experimental kinetic isotope effects are in accord with the mechanism derived from the computations. The computational results led to the development of Pd(II)-catalyzed [3,3]-sigmatropic rearrangement of 3-aryl substituted 2-propargylindoles. ...[more]

PMID: 30295492

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