Synthesis of Bis(3‐indolyl)methanes Mediated by Potassium tert‐Butoxide DOI Creative Commons
A. Sofia Santos,

Rita Ferro,

Nuno Viduedo

et al.

ChemistryOpen, Journal Year: 2023, Volume and Issue: 12(1)

Published: Jan. 1, 2023

The indole moiety is an important N-heterocycle found in natural products, and a key structural component of many value-added chemicals including pharmaceuticals. In particular, bis(3-indolyl)methanes (BIMs) are subgroup indoles, composed two units. Herein, we report the development simple method to access BIMs derivatives yields up 77 % by exploiting tBuOK-mediated coupling reaction indoles benzyl alcohols.

Language: Английский

Regioselective C3Alkylation of Indoles for the Synthesis of Bis(indolyl)methanes and 3-Styryl Indoles DOI
Ruiqin Zhang,

Renchao Ma,

Rener Chen

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(3), P. 1846 - 1857

Published: Jan. 12, 2024

Herein, we describe an efficient transition-metal-free regioselective C3alkylation of indoles for the synthesis bis(indolyl)methanes and 3-styryl indoles. Nitrobenzene is employed as oxidant to oxidize alcohols in presence a strong base reaction avoids use transition metals such Ru Mn. The protocol provides favorable route access biologically active compounds arundine, vibrindole A, turbomycin B.

Language: Английский

Citations

18
Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds DOI
Sourajit Bera, Lalit Mohan Kabadwal, Debasis Banerjee

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Language: Английский

Citations

16
Transition metal-catalysis in interrupted borrowing hydrogen strategy DOI Creative Commons
Madhu Nallagangula, Murugan Subaramanian, Rohit Kumar

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(51), P. 7847 - 7862

Published: Jan. 1, 2023

This review article highlights the recent advances of transition-metal-catalyzed interrupted borrowing hydrogen (IBH) catalysis and its applications in sustainable affordable chemical synthesis using alcohols as C1 feedstocks.

Language: Английский

Citations

34
Multi-Functionality of Methanol in Sustainable Catalysis: Beyond Methanol Economy DOI
Ganesan Sivakumar, Rohit Kumar, Vinita Yadav

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(22), P. 15013 - 15053

Published: Nov. 6, 2023

Methanol is a fundamental feedstock and widely used in the chemical petroleum industries. It can serve as C1 source to make variety of C–C C–N bond formation dehydrogenative coupling products, which have important applications natural products drug discovery. A high hydrogen content (12.5 wt%) methanol makes it an effective H2 donor for transfer hydrogenation various reducible functional groups. plethora transition metal-based processes been developed using methanol. Notably, recent review articles focused on aspect However, more updated that examines challenges both C1-source H2-source organic transformations contributing concept economy has not presented yet. This Review summarizes (homogeneous, heterogeneous, photo-) catalyst system C-, N-, O-methylation ketones, alcohols, amides, nitriles, heterocyclic compounds, sulfones, amines, sulfonamides direct N-methylation nitro compounds under borrowing strategy N-formylation amines acceptorless dehydrogenation source. also covers insights into reaction mechanisms role carefully selected ligands metal catalysis activation incorporation -CD3, methylation molecules. Moreover, describes groups such aldehydes, alkynes, with detail.

Language: Английский

Citations

28
Nickel-catalysed chemoselective C-3 alkylation of indoles with alcohols through a borrowing hydrogen method DOI

Amreen K. Bains,

Ayanangshu Biswas, Debashis Adhikari

et al.

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(98), P. 15442 - 15445

Published: Jan. 1, 2020

A nickel catalysed chemoselective C3-alkylation of indole is reported that follows a borrowing hydrogen method promoted by radical.

Language: Английский

Citations

65
C-Alkylation of Various Carbonucleophiles with Secondary Alcohols under CoIII-Catalysis DOI
Priyanka Chakraborty, Nidhi Garg, Éric Manoury

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(14), P. 8023 - 8031

Published: June 26, 2020

Oxindoles have been successfully α-alkylated under Cp*CoIII catalysis by a vast array of secondary alcohols, including cyclic, acyclic, symmetrical, and unsymmetrical, to produce C-alkylated oxindoles. This protocol was also extended the α-alkylation N,N-dimethyl barbituric acid benzyl cyanides. The kinetic profile other preliminary mechanistic investigations suggest first-order reaction rate in oxindoles catalysts. A plausible catalytic cycle is proposed on basis profile, investigations, previous studies similar transformations, whereas density functional theory calculations provide insight into nature active species.

Language: Английский

Citations

55
Ru-Catalyzed Selective Catalytic Methylation and Methylenation Reaction Employing Methanol as the C1 Source DOI
Nandita Biswas, Dipankar Srimani

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(15), P. 10544 - 10554

Published: July 15, 2021

Methanol can be employed as a green and sustainable methylating agent to form C–C C–N bonds via borrowing hydrogen (BH) methodology. Herein we explored the activity of acridine-derived SNS-Ru pincer for activation methanol apply it C1 building block in different reactions. Our catalytic system shows great success toward β-C(sp3)-methylation reaction 2-phenylethanols provide good excellent yields methylated products. We investigated mechanistic details, kinetic progress, temperature-dependent product distribution, which revealed slow steady generation situ formed aldehyde, is key factor get higher yield β-methylated product. To establish environmental benefit this reaction, chemistry metrics are calculated. Furthermore, dimerization 2-naphthol methylene linkage formation N-methylation amine also described study, offers wide range substrate scope with yield.

Language: Английский

Citations

50
Well-Defined NNS-Mn Complex Catalyzed Selective Synthesis of C-3 Alkylated Indoles and Bisindolylmethanes Using Alcohols DOI
Avijit Mondal, Rahul Sharma, Bishal Dutta

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(6), P. 3989 - 4000

Published: March 8, 2022

Herein, we demonstrated Mn-catalyzed selective C-3 functionalization of indoles with alcohols. The developed catalyst can also furnish bis(indolyl)methanes from the same set substrates under slightly modified reaction conditions. Mechanistic studies reveal that is going via a borrowing hydrogen pathway. To highlight practical utility, diverse range including nine structurally important drug molecules are synthesized. Furthermore, introduced one-pot cascade strategy for synthesizing functionalized directly 2-aminophenyl ethanol and alcohol.

Language: Английский

Citations

36
N-Alkylation of Amines by C1–C10 Aliphatic Alcohols Using A Well-Defined Ru(II)-Catalyst. A Metal–Ligand Cooperative Approach DOI
Amit Kumar Guin, Subhasree Pal, Subhajit Chakraborty

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5944 - 5961

Published: April 13, 2023

A Ru(II)-catalyzed efficient and selective N-alkylation of amines by C1-C10 aliphatic alcohols is reported. The catalyst [Ru(L1a)(PPh3)Cl2] (1a) bearing a tridentate redox-active azo-aromatic pincer, 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (L1a) air-stable, easy to prepare, showed wide functional group tolerance requiring only 1.0 mol % (for N-methylation N-ethylation) 0.1 loading for with C3-C10 alcohols. array N-methylated, N-ethylated, N-alkylated were prepared in moderate good yields via direct coupling 1a efficiently catalyzes the diamines selectively. It even suitable synthesizing using (aliphatic) diols producing tumor-active drug molecule MSX-122 yield. excellent chemo-selectivity during oleyl alcohol monoterpenoid β-citronellol. Control experiments mechanistic investigations revealed that 1a-catalyzed reactions proceed borrowing hydrogen transfer pathway where removed from dehydrogenation step stored ligand backbone 1a, which subsequent steps transferred situ formed imine intermediate produce amines.

Language: Английский

Citations

22
Alcohol Dehydrogenation-Triggered Selective C3-Alkylation of Indoles by Homogeneous Azo-aromatic Cobalt Catalysts DOI

kamal kamal,

Manas Khatua, Swati Rani

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(9), P. 5827 - 5843

Published: April 10, 2023

Herein, we report azo-benzimidazole containing cobalt complexes (1-3) for alcohol dehydrogenation-triggered C3-alkylation of indoles. In 1-3, ligands are redox noninnocent and showed facile irreversible L/L• reduction followed by Co(II)/Co(I) in close-lying potentials. Taking advantage events the first aerial dehydrogenation alcohols to their corresponding carbonyl compounds is explored. Subsequently, indole was studied using as alkylating agents. The developed catalytic protocol found be efficient very selective. It has a broad substrate scope good functional group tolerance. As far aware, it homogeneous catalyst agent. Detailed mechanistic studies, including deuterium labeling experiment, have suggested borrowing hydrogen method indole. coordinated ligand, cooperatively with couple, oxidized alkoxide radical pathway result compound (Scheme 1), which on subsequent condensation generates alkylideneindolenine intermediate "X". Reduction "X" an azo-anion Co(I) resulted C3-alkylated

Language: Английский

Citations

21