Mechanistic Insights into Cobalt-Catalyzed Regioselective C4-Alkenylation of 3-Acetylindole: A Detailed Theoretical Study DOI
Jinfeng Li, Bing Yin, Ji‐Jiang Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(21), P. 14125 - 14136

Published: Oct. 18, 2022

A detailed mechanistic study of Co(III)-catalyzed C4-alkenylation 3-acetylindole (1a) was done based on calculations at density functional theory (DFT) and correlated wave function levels. The whole catalytic cycle consists four steps: C-H activation, olefin insertion, β-hydride elimination, regeneration the catalyst. theoretical results support insertion as rate-determining step leading to experimentally observed regioselectivity C4 site over C2 site. By analysis three-dimensional (3D) geometries NCl plot, preference for could be attributed weaker repulsive interaction between indole moiety in transition states former. reliability is further confirmed through DFT calculation other related derivatives substrates.

Language: Английский

Recent advances in the accessibility, synthetic utility, and biological applications of aziridines DOI Creative Commons
Christian Dank, Laura Ielo

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(22), P. 4553 - 4573

Published: Jan. 1, 2023

Compounds featuring aziridine moieties are widely known and extensively reported in the literature. Due to their great potential from both synthetic pharmacological points of view, many researchers have focused efforts on development new methodologies for preparation transformation these interesting compounds. Over years, more ways obtain molecules bearing three-membered functional groups, which challenging due inherent reactivity, been described. Among them, several sustainable. In this review, we report recent advances biological chemical evolution derivatives, particular, variety described synthesis aziridines transformations leading formation such as 4-7 membered heterocycles pharmaceutical interest promising activities.

Language: Английский

Citations

35
Nickel-Catalyzed Rearranged Alkenylation of 2-Arylaziridines with Aryl Alkenes to Access Allylamines DOI
Xiangkai Kong,

Ming-Bai Gou,

Bo Li

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

The transition-metal-catalyzed ring-opening functionalization of aziridines presents a promising approach for synthesizing structurally complex amines. However, the rearranged poses significant challenges. Herein, we report first alkenylation with aryl alkenes via Ni-Brønsted acid co-catalysis, leading to rapid synthesis diverse array allylamines yields reaching up 91%. Mechanistic studies suggest that reaction occurs through rearrangement aziridine generate an imine intermediate. This intermediate is subsequently captured by alkene under nickel catalysis, ultimately formation allylamines.

Language: Английский

Citations

1
Transition-Metal-Catalyzed Directed C8–H Carbon–Carbon Bond Formation in Quinolines and 1,2,3,4-Tetrahydroquinolines DOI
Tharmalingam Punniyamurthy, Shubhajit Basak, Tripti Paul

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 55(21), P. 3454 - 3469

Published: March 20, 2023

Abstract C8-Substituted quinoline (QN) and 1,2,3,4-tetrahydroquinoline (THQ) scaffolds are featured in numerous bioactive compounds natural products. Appreciable efforts have been made towards the development of elegant techniques to functionalize C8–H bond QNs THQs. The transition-metal-catalyzed chelation-assisted C–H activation strategy has emerged as an effective synthetic tool among existing methods. This review focuses on recent advances directed carbon–carbon forming reactions for functionalization THQs (till February 2023). discussion categorized based type reaction. 1 Introduction 2 Acylation 3 Alkylation 4 Alkenylation 5 Alkynylation 6 Allylation 7 Annulation 8 Arylation 9 Conclusion Outlook

Language: Английский

Citations

7
Electrochemically Driven Selective Removal of the S═N Bond-Directing Group Using Cyclohexanone Oxime as the Mediator DOI
Zhicheng Xiong, Hongsheng Nie, Shuai Zhang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(7), P. 4334 - 4344

Published: March 16, 2023

An inexpensive electrochemical induction system was used for the efficient reductive defunctionalization of sulfoximines through a radical pathway. This practical and robust strategy could be removal S═N bond-directing group from various sulfoximines. The practicability this method demonstrated by its mild conditions, simple operation, one-pot procedure, gram-scale synthesis, undivided cell. Furthermore, preliminary mechanistic studies suggested that reaction might proceed via homocoupling denitrification procedure.

Language: Английский

Citations

6
Transition-Metal-Catalyzed Directing-Group-Assisted C4-H Carbon–Carbon Bond Formation of Indole DOI
Tharmalingam Punniyamurthy, Shubhajit Basak, Tripti Paul

et al.

Synlett, Journal Year: 2022, Volume and Issue: 34(07), P. 759 - 776

Published: Aug. 19, 2022

Abstract C4-Functionalized indole scaffolds are ubiquitous in natural products, bioactive compounds, and pharmaceuticals. Much effort has thus been made to develop effective synthetic strategies for C4 functionalization of the core. Among them, chelation-assisted approaches using transition-metal catalysis C4-selective C–H is attractive. This account highlights progress C4-carbon–carbon bond formation directing-group-assisted transition-metal-catalyzed (up May 2022). These studies have performed Ru, Rh, Pd Ir-based catalytic systems, while attention focused on use first-row abundant systems. 1 Introduction 2 Alkylation 3 Acylation 4 Alkenylation 5 Alkynylation 6 Allylation 7 Annulation 8 Arylation 9 Conclusion Outlook

Language: Английский

Citations

6
Directing Group Guided Site−Selective Alkylation of Indoles by Epoxides: Synthesis of β‐Indolylethyl Alcohol Derivatives DOI
Ashfaq Ahmad, Mohit Kumar,

Anushka Rastogi

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(21), P. 4416 - 4421

Published: Aug. 7, 2024

Abstract A Palladium catalyzed C4‐ alkylation of indoles using epoxide as an alkylating agent and pivaloyl a weak chelating group has been demonstrated. variety substituted epoxides furnished the desired β‐indolylethyl alcohols in 38%–87% yields. Control experiments indicate that C−H cleavage step is irreversible. The resultant hydroxyl converted to various functional groups demonstrate synthetic utility this protocol.

Language: Английский

Citations

0
Weakly coordinating tert-amide assisted Rh(iii)-catalyzed C4-cyanation of indoles: application in photophysical studies DOI

Souradip Sarkar,

Aniruddha Biswas,

Sarbojit Das

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(75), P. 11200 - 11203

Published: Jan. 1, 2023

A rhodium(III)-catalyzed indole C4-selective cyanation is described using the bench-stable, user-friendly electrophilic agent N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) as a coupling partner. suitably positioned weakly coordinating tert-amide group was utilized for this site selectivity. The developed protocol proceeded with broad scope. [Cp*Rh(MeCN)3][SbF6]2 found to be an effective Rh(III) catalyst transformation. An initial study carried out know photophysical properties of C4-cyanated frameworks.

Language: Английский

Citations

1
Five-membered ring systems: pyrroles and benzo analogs DOI
Justin M. Lopchuk

Progress in heterocyclic chemistry, Journal Year: 2023, Volume and Issue: unknown, P. 199 - 250

Published: Jan. 1, 2023

Language: Английский

Citations

1
Mechanistic Insights into Cobalt-Catalyzed Regioselective C4-Alkenylation of 3-Acetylindole: A Detailed Theoretical Study DOI
Jinfeng Li, Bing Yin, Ji‐Jiang Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(21), P. 14125 - 14136

Published: Oct. 18, 2022

A detailed mechanistic study of Co(III)-catalyzed C4-alkenylation 3-acetylindole (1a) was done based on calculations at density functional theory (DFT) and correlated wave function levels. The whole catalytic cycle consists four steps: C-H activation, olefin insertion, β-hydride elimination, regeneration the catalyst. theoretical results support insertion as rate-determining step leading to experimentally observed regioselectivity C4 site over C2 site. By analysis three-dimensional (3D) geometries NCl plot, preference for could be attributed weaker repulsive interaction between indole moiety in transition states former. reliability is further confirmed through DFT calculation other related derivatives substrates.

Language: Английский

Citations

1