Ruthenium(II)-Catalyzed Direct C7-Selective Amidation of Indoles with Dioxazolones at Room Temperature DOI

Yaoguang Sheng,

Jianmin Zhou, Yi Gao

et al.

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(3), P. 2827 - 2839

Published: Jan. 20, 2021

A protocol for the preparation of 7-amido indoles via regioselective C–H bond functionalization has been first accomplished under Ru(II) catalysis. Indole derivatives and 4-aryl/heteroaryl/benzyl/alkyl dioxzaolines containing various substituents were applicable this transformation, readily providing amidated in moderate to good yields. This novel process many advantages, including compatibility with diverse functional groups, broad substrate scopes, mild reaction conditions. Deuteration studies control experiments have performed understand mechanism transformation.

Language: Английский

Installing the “magic methyl” – C–H methylation in synthesis DOI Creative Commons
Daniya Aynetdinova, Mia Callens, Harry B. Hicks

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(9), P. 5517 - 5563

Published: Jan. 1, 2021

Following notable cases of remarkable potency increases in methylated analogues lead compounds, this review documents the state-of-the-art C–H methylation technology.

Language: Английский

Citations

185
From C4 to C7: Innovative Strategies for Site-Selective Functionalization of Indole C–H Bonds DOI

Jian Wen,

Zhuangzhi Shi

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(7), P. 1723 - 1736

Published: March 12, 2021

The widespread presence of hydrocarbons makes C-H functionalization an attractive alternative to traditional cross-coupling methods. As indole is important heteroarene in a plethora natural products and pharmaceuticals, moieties has emerged as one the most topics this field. Due multiple bonds indoles, site selectivity long-standing challenge. Much effort been devoted indoles at C3 or C2 position, while accessing benzene core (from C4 C7) considerably more challenging.This Account summarizes our recent efforts toward site-selective based on innovative strategies. A common method solve issue involves development directing groups (DGs). Our early studies establish that installation N-P(O)tBu2 group N position can produce C7 C6 arylation using palladium copper catalysts, respectively. developed system also be extended direct C5 positions by installing pivaloyl position. Further investigation bearing N-PtBu2 shows diverse reactivity for functionalizations including arylation, olefination, acylation, alkylation, silylation, carbonylation with different coupling partners. Compared P(V) DG, P(III) easily attached substrates detached from products. However, these reactions rely mostly precious metal catalysts ligands; requirement significant limitation, particularly large-scale syntheses necessity removal toxic trace metals pharmaceutical We have uncovered general strategy chelation-assisted aromatic borylation just simple BBr3 under mild conditions, which N1 selectively deliver boron species unfavorable allow subsequent without any metal. This transition-metal-free synthesize hydroxylated boron-mediated directed hydroxylation reaction conditions broad functional compatibility.In Account, we describe contributions topic since 2015. These provide efficient methods divergent synthesis valuable substituted insights into exploration new strategies directives other heteroarenes.

Language: Английский

Citations

179
Site-selective C–H functionalization to access the arene backbone of indoles and quinolines DOI
B. Prabagar, Youqing Yang, Zhuangzhi Shi

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(20), P. 11249 - 11269

Published: Jan. 1, 2021

The site-selective C-H bond functionalization of heteroarenes can eventually provide chemists with great techniques for editing and building complex molecular scaffolds. During the past decade, benzo-fused N-heterocycles such as indoles quinolines have been among most widely investigated organic templates. Early developments led to on pyrrole pyridine cores quinolines; however, benzenoid ring has remained a challenge in catalysis. In this review, we elaborate recent highly challenging bonds less-reactive core quinolines. These findings are mainly described selective directing group assisted strategies, remote their reaction mechanisms. underlying principle each strategy is elucidated, which aims facilitate design more advanced structure heterocycles based bioactive molecules, synthetic drugs, material aspects. Moreover, challenges perspectives catalytic access arene backbone also proposed conclusion section.

Language: Английский

Citations

166
Recent Advances in Metal‐Catalyzed Functionalization of Indoles DOI

Kelvin Urbina,

David S. Tresp, Karli Sipps

et al.

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(11), P. 2723 - 2739

Published: April 7, 2021

Abstract Indole is one of the most important heterocycles in organic synthesis, natural products, and drug discovery. Recently, tremendous advances selective functionalization indoles have been reported. Although powered by transition metal catalysis, exceedingly useful methods absence metals also In this review, we provide an overview reactions that published last years with a focus on recent advances, aims, future trends. The review organized positional selectivity type used for functionalization. particular, discuss major transition‐metal‐catalyzed C−H at classical C2/C3 positions, remote C4/C7 cross‐coupling, transition‐metal‐free magnified image

Language: Английский

Citations

127
Tunable molecular editing of indoles with fluoroalkyl carbenes DOI
Shaopeng Liu, Yong Yang, Qingmin Song

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(6), P. 988 - 997

Published: March 5, 2024

Language: Английский

Citations

40
Tryptophan-specific modification and diversification of peptides and proteins DOI
S K Kundu, A. Bandyopadhyay, Rajib Sarkar

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review provides an account of the tryptophan-specific conjugation peptides and proteins its extensive application in imaging living cells, radiolabelling proteins, protein engineering, etc .

Language: Английский

Citations

2
C7‐Indole Amidations and Alkenylations by Ruthenium(II) Catalysis DOI Creative Commons
Isaac Choi, Antonis M. Messinis, Lutz Ackermann

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(30), P. 12534 - 12540

Published: June 2, 2020

C7-H-functionalized indoles are ubiquitous structural units of biological and pharmaceutical compounds for numerous antiviral agents against SARS-CoV or HIV-1. Thus, achieving site-selective functionalizations the C7-H position indoles, while discriminating among other bonds, is in high demand. Herein, we disclose activations by ruthenium(II) biscarboxylate catalysis under mild conditions. Base-assisted internal electrophilic-type substitution C-H ruthenation weak O-coordination enabled functionalization offered a broad scope, including C-N C-C bond formation. The versatile ruthenium-catalyzed were characterized gram-scale syntheses traceless removal directing group, thus providing easy access to pharmaceutically relevant scaffolds. Detailed mechanistic studies through spectroscopic spectrometric analyses shed light on unique nature robust ruthenium indoles.

Language: Английский

Citations

82
Peptide Late-Stage Diversifications by Rhodium-Catalyzed Tryptophan C7 Amidation DOI Creative Commons
Wei Wang, Jun Wu, Rositha Kuniyil

et al.

Chem, Journal Year: 2020, Volume and Issue: 6(12), P. 3428 - 3439

Published: Nov. 20, 2020

Language: Английский

Citations

72
Recent Advances in Metal‐catalyzed Alkylation, Alkenylation and Alkynylation of Indole/indoline Benzenoid Nucleus DOI
Sourav Pradhan,

Pinaki Bhusan De,

Tariq A. Shah

et al.

Chemistry - An Asian Journal, Journal Year: 2020, Volume and Issue: 15(24), P. 4184 - 4198

Published: Nov. 9, 2020

Selective editing of the benzenoid C-H bonds (C4-C7) in indoles/indolines has received great interest because functionalized are featured many marketed drugs and natural products. Transition-metal-catalyzed directed functionalization thus been developed to manipulate core through C-C C-heteroatom bond formation. This review covers recent advances selective forming reactions, alkylation, alkenylation alkynylation, over ring using metal catalysis.

Language: Английский

Citations

56
Iron-Catalyzed Highly para-Selective Difluoromethylation of Arenes DOI

Wei‐Tai Fan,

Yuting Li, Dongjie Wang

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(49), P. 20524 - 20530

Published: Nov. 30, 2020

Direct functionalization of a C-H bond at either the meta or para position by only changing catalyst system poses significant challenge. We herein report [Fe(TPP)Cl]-enabled, selective, difluoromethylation arenes using BrCF2CO2Et as source, which successfully altered selectivity from to position. A preliminary mechanistic study revealed iron porphyrin complex not activated aromatic ring but also induced due influence ligand sterics.

Language: Английский

Citations

54