Who is Who in the Carbene Chemistry of N‐Sulfonyl Hydrazones DOI
Paramasivam Sivaguru,

Yongzhen Pan,

Nan Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(17), P. 2071 - 2108

Published: May 27, 2024

Comprehensive Summary Over the past few decades, N ‐sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis, allowing diverse innovative and original chemical transformations that were otherwise difficult to achieve. This critical review summarizes major advancements carbene chemistry of hydrazones. The contents this are organized based on research conducted by leading scientists who made significant contributions field. individual transfer reactions their mechanisms, well potential applications synthesis natural products complex bioactive molecules, thoroughly discussed.

Language: Английский

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

46
Dearomatization of Pyridines: Photochemical Skeletal Enlargement for the Synthesis of 1,2-Diazepines DOI

Elise Boudry,

Flavien Bourdreux,

Jérôme Marrot

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2845 - 2854

Published: Jan. 18, 2024

In this report, we developed a unified and standardized one-pot sequence that converts pyridine derivatives into 1,2-diazepines by inserting nitrogen atom. This skeletal transformation capitalizes on the in situ generation of 1-aminopyridinium ylides, which rearrange under UV light irradiation. A thorough evaluation key parameters (wavelength, reaction conditions, activating agent) allowed us to elaborate simple, mild, user-friendly protocol. The model was extrapolated more than 40 examples, including drug derivatives, affording unique 7-membered structures. Mechanistic evidence supports transient presence diazanorcaradiene species. Finally, pertinent transformations products, ring contraction reactions form pyrazoles, were conducted paved way broad application

Language: Английский

Citations

35
The Carbene Chemistry of N-Sulfonyl Hydrazones: The Past, Present, and Future DOI
Xiaolong Zhang, Paramasivam Sivaguru,

Yongzhen Pan

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

N-Sulfonyl hydrazones have been extensively used as operationally safe carbene precursors in modern organic synthesis due to their ready availability, facile functionalization, and environmental benignity. Over the past two decades, there has tremendous progress chemistry of N-sulfonyl presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Many transfer reactions are unique cannot be achieved by any alternative methods. The discovery novel development highly enantioselective new skeletal editing represent notable recent achievements hydrazones. This review describes overall made hydrazones, organized based on reaction types, spotlighting current state-of-the-art remaining challenges addressed future. Special emphasis is devoted identifying, describing, comparing scope limitations methodologies, key mechanistic scenarios, potential applications complex molecules.

Language: Английский

Citations

6
Rhodium‐Catalyzed One‐Carbon Ring Expansion of Aziridines with Vinyl‐N‐triftosylhydrazones for the Synthesis of 2‐Vinyl Azetidines DOI
Yongquan Ning,

Hongzhu Chen,

Yongyue Ning

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(12)

Published: Jan. 29, 2024

Abstract Azetidines, being four‐membered N ‐heterocycles, possess significant potential in contemporary medicinal chemistry owing to their favorable pharmacokinetic properties. Regrettably, the incorporation of functionalized azetidines into pharmaceutical lead structures has been impeded by absence efficient synthetic methods for synthesis. In this study, a Rh‐catalyzed one‐carbon ring expansion aziridines with vinyl‐ ‐triftosylhydrazones is presented, which facilitates synthesis high value‐added 2‐alkenyl azetidine products. This research represents first example enabled vinyl carbenes. Additionally, one‐pot two‐step protocol, initiated from cinnamaldehyde, was successfully achieved, offering step‐economical and facile approach these compounds. The pivotal aspect successful transformation lies situ formation an alkenyl aziridinium ylide intermediate. Experimental investigations, coupled computational studies, suggest that diradical pathway involved reaction mechanism.

Language: Английский

Citations

16
Photochemical Skeletal Editing of Pyridines to Bicyclic Pyrazolines and Pyrazoles DOI

Jiajing Luo,

Qingyang Zhou, Xu Zhou

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21389 - 21400

Published: June 14, 2024

We present an efficient one-pot photochemical skeletal editing protocol for the transformation of pyridines into diverse bicyclic pyrazolines and pyrazoles under mild conditions. The method requires no metals, photocatalysts, or additives allows selective removal specific carbon atoms from pyridines, allowing unprecedented versatility. Our approach offers a convenient means late-stage modification complex drug molecules by replacing core pyridine skeleton. Moreover, we have successfully scaled up this procedure in stop-flow flow-chemistry systems, showcasing its applicability to intricate transformations such as Diels–Alder reaction, hydrogenation, [3 + 2] cycloaddition, Heck reaction. Through control experiments DFT calculations, provide insights mechanistic underpinnings protocol.

Language: Английский

Citations

16
Synthesis of benzenes from pyridines via N to C switch DOI Creative Commons

Aífe Conboy,

Michael F. Greaney

Chem, Journal Year: 2024, Volume and Issue: 10(6), P. 1940 - 1949

Published: June 1, 2024

The skeletal editing of heteroarenes introduces new disconnections to the chemistry lexicon, enabling interconversion ring systems via selective breaking/re-making carbon framework. We describe one-pot transformation pyridines into benzene derivatives, using a nucleophilic addition ring-opening/ring-closing (ANRORC) process with soft nucleophiles such as malonate. Triflic anhydride activates pyridine ANRORC synthesis an isolable amine intermediate, which aromatizes on simple heating. reaction has been exemplified room temperature protocol, along direct syntheses drug-like, tertiary-alkylated, and isotopically labeled benzoates.

Language: Английский

Citations

15
Triftosylhydrazone in Single-Atom Skeletal Editing DOI
Zhaohong Liu, Xiaolong Zhang, Paramasivam Sivaguru

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 16, 2024

ConspectusIn the past decade, single-atom skeletal editing, which involves precise insertion, deletion, or exchange of single atoms in core skeleton a molecule, has emerged as promising synthetic strategy for rapid construction diversification complex molecules without laborious de novo processes. Among them, carbene-initiated editing is particularly appealing due to ready availability and diverse reactivities carbene species. The initial endeavors modify heteroarenes through carbon-atom insertion could date back 1881, when Ciamician Denstedt described conversion pyrroles pyridines by trapping haloform-derived free carbene. Despite its potential value, general applicability this one-carbon seen limited progress poor yields harsh reaction conditions. Significant advances via were achieved only 3 years Levin, Ball, Xu, Song, Glorius, others. hallmark these approaches facile halocyclopropanation followed regioselective ring opening facilitated expulsion halide ion. Consequently, specially designed α-halocarbene precursors, such haloform derivatives, α-halodiazoacetates, chlorodiazirines, α-chlorodiazo oxime esters, can be employed achieve Ciamician–Denstedt-type editing. This not limits types functional groups installed on expansion products but also prevents their widespread adoption, especially late-stage contexts. enduring quest develop environmentally friendly versatile superior group compatibility, application diversifications investigation mechanistic insights into carbon reactions remain fundamental objective.In our over 5 years, we have developed o-trifluoromethylbenzenesulfonylhydrazones (named Triftosylhydrazones) operationally safe easily decomposable diazo surrogates explored various challenging catalytic transfer reactions. Recently, put great efforts expanding scope unlocking triftosylhydrazones precursors Since 2018, realized range acyclic 1,3-dicarbonyls with silver carbenes access 1,4-dicarbonyls, proceeding cyclopropanation/ring-opening process. Inspired results, recently demonstrated series transition-metal-catalyzed highly selective medicinally interesting like pyrroles, indoles, 1,2-diazoles carbenic insertion. We then strained three-membered nitrogen- oxygen-containing heterocycles single-carbon atoms. In Account, present an overview achievements heterocycles, organized based three situ-generated key intermediates, cyclopropane, N-ylide, O-ylide from focus scopes, features, applications. hope that Account will provide valuable contribute development new methodologies both chemistry fields.

Language: Английский

Citations

15
Reactivity of α-diazo sulfonium salts: rhodium-catalysed ring expansion of indenes to naphthalenes DOI Creative Commons

Sven Timmann,

Tun-Hui Wu,

Christopher Golz

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(16), P. 5938 - 5943

Published: Jan. 1, 2024

Cyclopropyl-substituted sulfonium salts are obtained by Rh-catalysed addition of α-diazo dibenzothiophenium to olefins. When indenes used as substrates, initially formed cyclopropyl rings open with concomitant elimination dibenzothiophene, enabling access 2-substituted naphthalenes.

Language: Английский

Citations

13
Asymmetric dearomative single-atom skeletal editing of indoles and pyrroles DOI
Xiaolong Zhang, Qingmin Song, Shaopeng Liu

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Language: Английский

Citations

13
N‐Heterocycle‐Editing to Access Fused‐BN‐Heterocycles via Ring‐Opening/C−H Borylation/Reductive C−B Bond Formation DOI
Xu Zhang,

Wanlan Su,

Huosheng Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 10, 2024

Skeletal editing of N-heterocycles has recently received considerable attention, and the introduction boron atom into heterocycles often results in positive property changes. However, direct enlargement through insertion is rarely reported literature. Here, we report a N-heterocyclic reaction combination C-H borylation, accessing fused-BN-heterocycles. The synthetic potential this chemistry was demonstrated by substrate scope late-stage diversification products.

Language: Английский

Citations

12