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

Yan-Zheng Sun,

Hucheng Yang,

Jun‐Rong Song

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(22)

Опубликована: Ноя. 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.

Язык: Английский

Benzylic C(sp3)–H Functionalization via Copper-Catalyzed [3+3] Radical Cycloaddition DOI
Jun Shi,

Xiong-Jiang Li,

Shu-Yun Jiang

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 5605 - 5611

Опубликована: Март 29, 2024

The development of benzylic C(sp3)–H functionalization methods for the assembly derivatives has been extensively explored in recent years. However, engagement carbon and its adjacent C=C bond as a C3 synthon cycloaddition reaction via direct C–H activation is rare. Herein, we report copper-catalyzed [3+3] radical through to construct six-membered cyclohexane-type rings. In this reaction, 2-benzylic an indole selectively activated serves that reacts highly chemoselective intermolecular self-[3+3] cross-[3+3] pathways. Multiple symmetric nonsymmetric polycyclic hexahydrocarbazole scaffolds with hexacyclic 6/5/5/6/5/5/6 pentacyclic 6/5/5/6/5/6 ring systems are synthesized high efficiency chemoselectivity using strategy. Inspired by unique addition pathway cycloaddition, controllable construction C3a-alkylated pyrroloindolines was also developed.

Язык: Английский

Процитировано

6

Copper/Iodine Co-catalyzed Oxygenative Transannulation of Tryptamines Enables Direct Synthesis of Donaxaridine and Its Derivatives DOI

Yan-Zheng Sun,

Ying-Ai Wu,

Jun Shi

и другие.

Organic Letters, Год журнала: 2024, Номер 26(3), С. 625 - 630

Опубликована: Янв. 11, 2024

We report a general copper/iodine co-catalyzed oxygenative transannulation strategy using readily available tryptamines. Molecular oxygen and water are used as sources provide direct access to the donaxaridine scaffold its derivatives. This methodology is applied efficient synthesis of natural products donaxaridine, chimonamidine, donaxanine, donaxarine, aline in just one or two steps. The tryptamines, albeit with oxy-sensitive dialkyl N-H groups, selectively oxidized through single-electron transfer dioxygenation process.

Язык: Английский

Процитировано

5

Lewis-Base-Catalyzed Asymmetric Allylation of Isatins with Allyltrichlorosilane DOI

Yasemin Özkaya,

Frederic Ballaschk,

Christian Wagner

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Herein we report the enantioselective synthesis of 3-allyl-3-hydroxyoxindoles, a core scaffold in wide range bioactive molecules, using Lewis-base catalyst and readily abundant inexpensive allyltrichlorosilane. This transition-metal-free protocol employs relatively low loadings privileged bispyrrolidine-type to achieve high yields enantioselectivities (up 98% yield 98:2 er). The total syntheses natural products (−)-flustraminol B (−)-chimonamidine were also successfully carried out our newly developed method as key step, highlighting potential this for efficient precise complex products.

Язык: Английский

Процитировано

0

Asymmetric Cascade Dearomatization–Cyclization Reaction of Tryptamines with β,γ-Alkynyl-α-imino Esters: Access to Hexahydropyrrolo[2,3-b]indole-Containing Tetrasubstituted α-Amino Allenoates DOI

Chhavi Khajuria,

Nidhi Saini,

Parbat Subba

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 10148 - 10162

Опубликована: Июль 3, 2024

An organocatalytic enantio- and diastereoselective synthesis of hexahydropyrrolo[2,3-

Язык: Английский

Процитировано

2

Copper‐Catalyzed Tunable Oxygenative Rearrangement of Tetrahydrocarbazoles DOI
Hai Ren,

Bing‐Qing Yang,

Jun Shi

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(44)

Опубликована: Июнь 3, 2024

Herein, we report a general copper-catalyzed method for the tunable oxygenative rearrangement of tetrahydrocarbazoles to cyclopentyl-bearing spiroindolin-2-ones and spiroindolin-3-ones. The demonstrates excellent chemoselectivity, regioselectivity, product control simply by using H

Язык: Английский

Процитировано

1

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

Yan-Zheng Sun,

Hucheng Yang,

Jun‐Rong Song

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(22)

Опубликована: Ноя. 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.

Язык: Английский

Процитировано

0