Cobalt(III)-Catalyzed Free Amine Directed Site-Selective Allylation in 2-Aminobiaryls with Vinyl Cyclopropanes DOI Creative Commons
Deepan Chowdhury, Suman Ghosh, K. Satish Reddy

et al.

Published: April 12, 2023

2-Aminobiaryls are privileged scaffolds and their cogent synthesis diversifications, particularly through the C-H bond activation strategy, is a continuous enterprise in organic synthesis. In this realm, capitalization on susceptible native amine (-NH2) directing group beneficial but increasingly challenging owing to its innate nucleophilic reactivity. Also, reactions of class substrates have traditionally been restricted cross-ring as ortho functionalization presumably requires formation strained high-energy four-membered metallacycle. Herein, we report first example free amine-directed reaction 2-aminobiaryls under high-valent Cp*Co(III)-catalysis, enabling regio- stereoselective allylation high yields. The protocol engages vinyl cyclopropanes allyl synthons where C-C construction event was tunneled process forge internal olefin with exclusive (E)-selectivity. products were judicially used access high-value benzo[d]isoxazoles dihydro phenanthridine derivatives. Mechanistic experiments DFT calculations also conducted unravel rationale behind unique site selectivity, thermodynamic constraints corresponding intermediates favoring over functionalization.

Language: Английский

Predicting success in Cu-catalyzed C–N coupling reactions using data science DOI Creative Commons
Mohammad H. Samha, Lucas J. Karas, David B. Vogt

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(3)

Published: Jan. 17, 2024

Data science is assuming a pivotal role in guiding reaction optimization and streamlining experimental workloads the evolving landscape of synthetic chemistry. A discipline-wide goal development workflows that integrate computational chemistry data tools with high-throughput experimentation as it provides experimentalists ability to maximize success expensive campaigns. Here, we report an end-to-end data-driven process effectively predict how structural features coupling partners ligands affect Cu-catalyzed C–N reactions. The established workflow underscores limitations posed by substrates while also providing systematic ligand prediction tool uses probability assess when will be successful. This platform strategically designed confront intrinsic unpredictability frequently encountered deployment.

Language: Английский

Citations

25
Transition metal-catalyzed cross-coupling reactions of N-aryl-2-aminopyridines DOI Creative Commons
Fatemeh Doraghi,

Lina Rezainia,

Mohammad Hossein Morshedsolouk

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(2), P. 1134 - 1151

Published: Jan. 1, 2025

Due to the presence of pyridyl directing group, N-aryl-2-aminopyridines can quickly form stable complexes with metals, leading cyclization and functionalization reactions. A large number N-heterocycles nitrogen-based molecules be easily constructed via this direct atom-economical cross-coupling strategy. In review, we have highlighted transformations in various transition metal catalysts, such as palladium, rhodium, iridium, ruthenium, cobalt copper.

Language: Английский

Citations

1
Sn(OTf)2-Catalyzed (3 + 2) Cycloaddition/Sulfur Rearrangement Reaction of Donor–Acceptor Cyclopropanes with Indoline-2-thiones DOI
Yan Jiang, Haojie Ma,

Chen-Ying Zhai

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1672 - 1676

Published: Feb. 15, 2024

The (3 + 2) cycloaddition/sulfur rearrangement reaction of donor–acceptor cyclopropanes bearing a single keto acceptor with indoline-2-thiones has been realized. Under the catalysis Sn(OTf)2, series functionalized 3-indolyl-4,5-dihydrothiophenes were synthesized moderate to excellent yields.

Language: Английский

Citations

6
One-Pot Synthesis of Benzo[c]phenanthridine Alkaloids from 7-Azabenzonorbornadienes and Aryl Nitrones DOI

N. Aravindan,

Masilamani Jeganmohan

Organic Letters, Journal Year: 2023, Volume and Issue: 25(21), P. 3853 - 3858

Published: May 18, 2023

An efficient synthesis of benzo[c]phenanthridine alkaloids via a synergistic combination C-C bond formation and cycloaromatization reaction is described. Aryl nitrones react with 7-azabenzonorbornadienes in the presence Rh(III) catalyst, providing pharmaceutically useful derivatives good to moderate yields. Using this methodology, highly such as norfagaronine, norchelerythrine, decarine, norsanguinarine, nornitidine were prepared single step.

Language: Английский

Citations

8
AlCl3-mediated ring-opening reactions of indoline-2-thiones with acyl cyclopropanes, bi-cyclopropanes and spirocyclic cyclopropanes DOI
Haojie Ma, Ke Gao, Xuelong Wang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(31), P. 6312 - 6316

Published: Jan. 1, 2023

A series of indolylthio-functionalized ketones were constructed via a ring-opening reaction, and the linear could be further transformed into dihydro-2 H -thiepino[2,3- b ]indoles.

Language: Английский

Citations

6
Cobalt(III)-Catalyzed Free-Amine-Directed Site-Selective Allylation in 2-Aminobiaryls with Vinyl Cyclopropanes DOI
Deepan Chowdhury, Suman Ghosh, K. Satish Reddy

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 12543 - 12552

Published: Sept. 11, 2023

2-Aminobiaryls are privileged scaffolds, and their cogent synthesis diversifications, particularly through the C–H bond activation strategy, a continuous enterprise in organic synthesis. In this realm, capitalizing on susceptible native amine (−NH2) directing group is beneficial but increasingly challenging owing to its innate nucleophilic reactivity. Additionally, reactions of class substrates have traditionally been restricted cross-ring bond, as ortho-C–H functionalization presumably requires formation strained high-energy four-membered metallacycle. Herein, we report free-amine-directed reaction 2-aminobiaryls under high-valent Cp*Co(III)-catalysis, enabling regio- stereoselective allylation high yields. The protocol engages vinyl cyclopropanes allyl synthons, where C–C construction event tunneled process forge an internal olefin with exclusive (E)-selectivity. products were judicially used access high-value benzo[d]isoxazoles dihydrophenanthridine derivatives. Mechanistic experiments DFT calculations also conducted unravel rationale behind unique site selectivity, thermodynamic constraints corresponding intermediates favor over functionalization.

Language: Английский

Citations

6
Rh(III)-Catalyzed C–H Allylation of Aromatic Ketoximes with Vinylaziridines DOI

Jingjing Nie,

Zhong‐Xia Wang

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(8), P. 5764 - 5777

Published: April 5, 2024

The Rh(III)-catalyzed reaction of aromatic ketoximes with 2-vinylaziridines affords ortho-allylation products the phenyl rings in moderate to excellent yields. requires 0.5 equiv NaOAc as a base and occurs under mild conditions. protocol exhibits ortho-monoallylation selectivity, wide scope substrates, good compatibility functional groups.

Language: Английский

Citations

2
Recent updates on vinyl cyclopropanes, aziridines and oxiranes: access to heterocyclic scaffolds DOI

Kiruthika Nachimuthu,

Jothi L. Nallasivam

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(21), P. 4212 - 4242

Published: Jan. 1, 2024

This present review delineates the repertoire of vinyl cyclopropanes and their stuctural analogues to accomplish a wide array oxa-cycles, aza-cycles, thia-cycles under transition metal catalysis metal-free approaches from early 2019 date. The generation electrophilic π-allyl intermediates 1-3/1-5-dipolarophile chemistry originating VCPs are always green, step- atom-economical sustainable strategies in comparsion with prefunctionalized and/or C-H activation protocols. Here, strained ring-system extends its applicability by relieving strain undergo ring-expansion reaction 5-9 membered carbo- heterocyclic systems. availability chiral ligands has paved way realizing asymmetric synthetic transformations.

Language: Английский

Citations

2
Rhodium-catalyzed annulation for the construction of indole core: An update DOI
Suven Das, Arpita Dutta

Tetrahedron, Journal Year: 2023, Volume and Issue: 146, P. 133633 - 133633

Published: Sept. 11, 2023

Language: Английский

Citations

4
Ruthenium(II)-Catalyzed S(II)-Directed Aromatic C–H Allylation with Vinylaziridines DOI

Yu‐Tong Duan,

Zhong‐Xia Wang

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(23), P. 16076 - 16090

Published: Nov. 16, 2023

The ruthenium-catalyzed reaction of aryl methyl thioethers with vinylaziridines affords ortho-position mono- or bis-allylation products depending on substituents the phenyl rings sulfide substrates ratio reactants. also features mild conditions, good product yields, wide scope substrates, compatibility functional groups, and selective formation E-configurated C-C double bonds.

Language: Английский

Citations

4