Direct Synthesis of N-Fused Indoles Enabled by Copper-Catalyzed Aerobic Oxygenative Rearrangement DOI

Yan-Zheng Sun,

Hucheng Yang,

Jun‐Rong Song

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(22)

Published: Nov. 4, 2024

N-Fused indoles are typical N-heterocycles, which extensively found in natural products and bioactive molecules. Despite their importance, the synthesis of N-fused has not yet been fully developed. Herein, we report a direct, general unified copper-catalyzed aerobic oxygenative skeletal rearrangement strategy using readily available cyclic indole substrates, provides practical synthetic platform for rapid construction wide array scaffolds. This open-flask method features mild reaction conditions, high chemoselectivity, broad substrate scope (over 90 examples). The scaled-up versatile transformations various nucleophiles demonstrated scalability utility this protocol. Mechanistic studies revealed that, by involving unique single-electron transfer (SET)-induced oxygenation mechanism, tetrahydro-γ-carbolines proceeded via formal 1,3-migration rearrangement, while that tetrahydrocarbazoles Witkop–Winterfeldt/C–C cleavage cascade.

Language: Английский

Direct Synthesis of N-Fused Indoles Enabled by Copper-Catalyzed Aerobic Oxygenative Rearrangement DOI

Yan-Zheng Sun,

Hucheng Yang,

Jun‐Rong Song

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(22)

Published: Nov. 4, 2024

N-Fused indoles are typical N-heterocycles, which extensively found in natural products and bioactive molecules. Despite their importance, the synthesis of N-fused has not yet been fully developed. Herein, we report a direct, general unified copper-catalyzed aerobic oxygenative skeletal rearrangement strategy using readily available cyclic indole substrates, provides practical synthetic platform for rapid construction wide array scaffolds. This open-flask method features mild reaction conditions, high chemoselectivity, broad substrate scope (over 90 examples). The scaled-up versatile transformations various nucleophiles demonstrated scalability utility this protocol. Mechanistic studies revealed that, by involving unique single-electron transfer (SET)-induced oxygenation mechanism, tetrahydro-γ-carbolines proceeded via formal 1,3-migration rearrangement, while that tetrahydrocarbazoles Witkop–Winterfeldt/C–C cleavage cascade.

Language: Английский

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