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Stereoselective rhodium-catalyzed 2-C-H 1,3-dienylation of indoles: dual functions of the directing group.

ABSTRACT: A rhodium-catalyzed intermolecular highly stereoselective 1,3-dienylation at the 2-position of indoles with non-terminal allenyl carbonates has been developed by using 2-pyrimidinyl or pyridinyl as the directing group. The reaction tolerates many functional groups affording the products in decent yields under mild conditions. In addition to C-H bond activation, the directing group also played a vital role in the determination of Z-stereoselectivity for the C-H functionalization reaction with 4-aryl-2,3-allenyl carbonates, which is confirmed by the E-selectivity observed with 4-alkyl-2,3-allenyl carbonates. DFT calculations have been conducted to reveal that π-π stacking involving the directing 2-pyrimidinyl or pyridinyl group is the origin of the observed stereoselectivity. Various synthetic transformations have also been demonstrated.

SUBMITTER: Zhai Y

PROVIDER: S-EPMC8447931 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Stereoselective rhodium-catalyzed 2-C-H 1,3-dienylation of indoles: dual functions of the directing group.

Zhai Yizhan Y Zhang Xue X Ma Shengming S

Chemical science 20210721 34

A rhodium-catalyzed intermolecular highly stereoselective 1,3-dienylation at the 2-position of indoles with non-terminal allenyl carbonates has been developed by using 2-pyrimidinyl or pyridinyl as the directing group. The reaction tolerates many functional groups affording the products in decent yields under mild conditions. In addition to C-H bond activation, the directing group also played a vital role in the determination of Z-stereoselectivity for the C-H functionalization reaction w ...[more]

PMID: 34667543

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