Aromatic nitrogen scanning by ipso -selective nitrene internalization

Science, Journal Year: 2023, Volume and Issue: 381(6665), P. 1474 - 1479

Published: Sept. 28, 2023

Nitrogen scanning in aryl fragments is a valuable aspect of the drug discovery process, but current strategies require time-intensive, parallel, bottom-up synthesis each pyridyl isomer because lack direct carbon-to-nitrogen (C-to-N) replacement reactions. We report site-directable C-to-N reaction allowing unified access to various pyridine isomers through nitrene-internalization process. In two-step, one-pot procedure, azides are first photochemically converted 3

Language: Английский

---

Synthesis of polysubstituted azepanes by dearomative ring expansion of nitroarenes

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(5), P. 771 - 779

Published: Jan. 25, 2024

Language: Английский

---

Light-promoted aromatic denitrative chlorination

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

Language: Английский

---

“Alkene-to-Alkene” Difunctionalization of Enaminones for the Synthesis of Polyfunctionalized Alkenes by Transition-Metal-Free C–H and C–N Bond Transformation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(47), P. 8451 - 8456

Published: Nov. 16, 2023

The three-component reactions of enaminones, disulfides, and alcohols for the synthesis polyfunctionalized alkenes have been realized via C-H C-N bond transformation on enaminones. proceed in a novel "alkene-to-alkene" difunctionalization mode without using any transition metal. application alkene products divergent sulfenyl heteroaryls, including sulfenylated pyrazoles, pyrimidines, isoxazoles, simple annulation has also verified.

Language: Английский

---

Recent progress in the synthesis of N-substituted arylamines by reductive cross-coupling of nitroarenes

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2638 - 2664

Published: Jan. 1, 2024

This review describes the recent advances in different reaction types and catalytic systems for construction of C–NAr S–NAr bonds by nitroaromatic reductive cross-coupling.

Language: Английский

---

Carbon–nitrogen transmutation in polycyclic arenol skeletons to access N-heteroarenes

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 4, 2024

Abstract Developing skeletal editing tools is not a trivial task, and realizing the corresponding single-atom transmutation in ring system without altering size even more challenging. Here, we introduce strategy that enables polycyclic arenols, highly prevalent motif bioactive molecules, to be readily converted into N -heteroarenes through carbon–nitrogen transmutation. The reaction features selective nitrogen insertion C–C bond of arenol frameworks by azidative dearomatization aryl migration, followed ring-opening, ring-closing (ANRORC) achieve carbon-to-nitrogen aromatic framework arenol. Using widely available arenols as -heteroarene precursors, this alternative approach allows streamlined assembly complex heteroaromatics with broad functional group tolerance. Finally, pertinent transformations products, including synthesis biheteroarene skeletons, were conducted exhibited significant potential materials chemistry.

Language: Английский

---

Precision single-atom editing: new frontiers in nitrogen insertion and substitution for the generation of N-heterocycles

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4041 - 4053

Published: Jan. 1, 2024

This paper primarily focuses on the editing of nitrogen atoms, encompassing insertion N, substitution C with and utilization 15 N in place 14 for construction N-heterocycles.

Language: Английский

---

A strategy for ortho-phenylenediamine synthesis via dearomative-rearomative coupling of nitrobenzenes and amines

Chem, Journal Year: 2023, Volume and Issue: 9(12), P. 3685 - 3695

Published: Nov. 14, 2023

Ortho-phenylenediamines are aromatic molecules featuring two vicinal N-substituents with strong structural relevance to the development of bioactive materials. These derivatives currently prepared from ortho-halogenated nitrobenzenes via multistep synthetic sequences. Here, we report a conceptually different approach where and amines can be directly converted into ortho-phenylenediamines without need for ortho-halogenation following stepwise manipulation. This strategy occurs under simple blue light irradiation introduces an alternative retrosynthetic tactic whereby amine coupling partner "seems" displace nitro group that shifts its ortho position while being reduced amidated in one-pot process. Mechanistically, this process capitalizes on conversion corresponding single nitrenes, which undergo series N-insertion, electrocyclic ring expansion, addition, contraction en route ortho-phenylenediamines.

Language: Английский

---

Chiral Bisphosphine-Catalyzed Asymmetric Staudinger/aza-Wittig Reaction: An Enantioselective Desymmetrizing Approach to Crinine-Type Amaryllidaceae Alkaloids

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 14136 - 14148

Published: April 20, 2024

An unprecedented chiral bisphosphine-catalyzed asymmetric Staudinger/aza-Wittig reaction of 2,2-disubstituted cyclohexane-1,3-diones is reported, enabling the facile access a broad range cis-3a-arylhydroindoles in high yields with excellent enantioselectivities. The key to success this work relies on first application bisphosphine DuanPhos reaction. effective reductive system has been established address challenging PV═O/PIII redox cycle associated catalyst. In addition, comprehensive experimental and computational investigations were carried out elucidate mechanism Leveraging newly developed chemistry, enantioselective total syntheses several crinine-type Amaryllidaceae alkaloids, including (+)-powelline, (+)-buphanamine, (+)-vittatine, (+)-crinane, have accomplished remarkable conciseness efficiency.

Language: Английский

---

Transformative Reactions in Nitroarene Chemistry: Advances in C–N Bond Cleavage, Skeletal Editing, and N–O Bond Utilization

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

Published: Jan. 1, 2025

This review aims to provide a comprehensive overview of the expanding utility nitroarenes and their potential for future applications in synthetic organic chemistry.

Language: Английский

---