Stereoselective Rhodium-catalyzed 2-C-H 1,3-dienylation of Indoles: Dual Functions of the Directing Group

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Oct 20

PMID 34667543

Citations 2

Authors

Yizhan Zhai

Xue Zhang

Shengming Ma

Affiliations

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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 -stereoselectivity for the C-H functionalization reaction with 4-aryl-2,3-allenyl carbonates, which is confirmed by the -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.

Citing Articles

Stereoselective rhodium-catalyzed reaction of allenes with organoboronic reagents for diversified branched 1,3-alkadienes.

Wang W, Hong S, He W, Zhang X, Qian H, Ma S Nat Commun. 2024; 15(1):8344.

PMID: 39333494 PMC: 11437177. DOI: 10.1038/s41467-024-52209-5.

Pd-Catalyzed Heck-Type Reactions of Allenes for Stereoselective Syntheses of Substituted 1,3-Dienes.

Vine L, Schomaker J Chemistry. 2021; 28(1):e202103507.

PMID: 34727393 PMC: 8727505. DOI: 10.1002/chem.202103507.

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