Rh(II)-Catalyzed Selective C(sp3)–H/C(sp2)–H Bonds Cascade Insertion to Construct [6–8–6] Benzo-Fused Scaffold DOI Creative Commons
T.X. Yu,

Feifei Fang,

Haowen Shou

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 10, 2024

The fused eight-membered carbocycles (EMCs) play vital roles in the medicinal and biological investigations of many natural products marketed drugs. traditional synthesis [6-8-6] benzo-fused derivatives involves multistep reactions low yields, making development a one-step method more challenging work. Here, we present novel strategy for construction scaffold from propargyl diazoacetates substituted with benzyl-nitrogen heterocyclic ring via Rh(ll)-catalyzed carbene/alkyne metathesis (CAM) selective C-H bond insertion. This exhibits specific substrate scope, simple operation, mild reaction conditions, high atom efficiency. Mechanistically, process sequential CAM, 1,3-H-shift, intramolecular nucleophilic attack, C(sp

Language: Английский

Carbene Formation or Reduction of the Diazo Functional Group? An Unexpected Solvent‐Dependent Reactivity of Cyclic Diazo Imides DOI Creative Commons
Yaseen Hussain, Claire Empel, René M. Koenigs

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: July 28, 2023

The control of the reactivity diazo compounds is commonly achieved by choice a suitable catalyst, e.g. via stabilization singlet carbenes or radical intermediates. Herein, we report on light-promoted cyclic imides with thiols, where solvent results in two fundamentally different reaction pathways. In dichloromethane (DCM), carbene formed initially and engages cascade C-H functionalization/thiolation to deliver indane-fused pyrrolidines good excellent yields. When switching acetonitrile solvent, pathway shut down an unusual reduction compound occurs under otherwise identical conditions, aryl thiol acts as reductant. A combined set experimental computational studies was carried out obtain mechanistic understanding support that indane formation proceeds insertion triplet carbene, while electron transfer process.

Language: Английский

Citations

14
Silver-catalyzed synthesis of nitrogen heterocycles: recent advancements DOI
P. Devi, Mohan Neetha, Gopinathan Anilkumar

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(21), P. 4332 - 4357

Published: Jan. 1, 2023

Silver catalysis offers environmentally friendly and simple protocols to construct N-heterocycles. Inspired by its appeal, herein we have summarized developments in the silver-catalyzed synthesis of N-heterocycles since 2019.

Language: Английский

Citations

12
Catalytic 4-exo-dig carbocyclization for the construction of furan-fused cyclobutanones and synthetic applications DOI Creative Commons

Kemiao Hong,

Yi Zhou,

Haoxuan Yuan

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 11, 2023

Cyclobutanone is a strained motif with broad applications, while direct assembly of the aromatic ring fused cyclobutanones beyond benzocyclobutenone (BCB) skeletons remains challenging. Herein, we report Rh-catalyzed formal [3+2] annulation diazo group tethered alkynes involving 4-exo-dig carbocyclization process, providing straightforward access to furan-fused cyclobutanones. DFT calculations disclose that, by comparison competitive 5-endo-dig mainly due lower angle strain key sp-hybridized vinyl cationic transition state in cyclization step. Using less reactive catalysts Rh2(carboxylate)4 critical for high selectivity, which explained as catalyst-substrate hydrogen bonding interaction. This method proved successful previously inaccessible and unknown cyclobutanone scaffolds, can participate variety post-functionalization reactions versatile synthetic blocks. In addition, preliminary antitumor activity study these products indicates that some molecules exhibite significant anticancer potency against different human cancer cell lines.

Language: Английский

Citations

11
Catalytic alkane C–H functionalization by carbene insertion into unactivated C(sp3)–H bonds DOI

Yongzhen Pan,

Yeming Wang, Swastik Karmakar

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(13), P. 3777 - 3799

Published: Jan. 1, 2024

This review summarizes the developments in C–H functionalization of saturated hydrocarbons (C n H 2 +2 and C ) through catalytic carbene insertion into their bonds dated up to February 2024, based on categories types carbenes.

Language: Английский

Citations

4
Cyclization Through Dual C(sp3)−H Functionalization DOI
Masoud Sadeghi

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(17), P. 3542 - 3563

Published: July 11, 2024

Abstract C( sp 3 )−H functionalization methods have been widely employed in many organic transformations such as cyclization reactions, heterocycle synthesis, cross‐coupling protocols, and photochemical transformations. Among these transformations, reaction through offers a direct route to convert simple linear substrates complex products. There are three common modes of utilizing bonds reactions including single, double, dual functionalization. As the most challenging mode, refers converting two separate one molecule into desired C−Z which can be reactions. Cyclization via classified based on C−H reactivities. Therefore, categorized classes types activated‐activated, activated‐unactivated, unactivated‐unactivated bonds. Most published reports for involve activated‐activated However, number reported papers other has growing. This review focuses protocols used categorizes

Language: Английский

Citations

2
Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp3)−H Bond Insertion DOI Creative Commons
Àlex Díaz‐Jiménez, Roger Monreal‐Corona, Albert Poater

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(5)

Published: Nov. 8, 2022

The trapping of the elusive vinylogous position a vinyl carbene with an aliphatic C(sp3 )-H bond has been achieved for first time during silver-catalyzed carbene/alkyne metathesis (CAM) process. A Tpx -containing silver complex promotes generation donor-acceptor which triggers CAM, generating subsequent donor-donor species, then undergoes selective insertion, leading to synthesis new family benzoazepines. Density functional theory (DFT) calculations unveil reaction mechanism, allows proposing that C-H insertion takes place in stepwise manner, hydrogen shift being rate determining step.

Language: Английский

Citations

10
Asymmetric Acyclic 1,3-Difunctionalization of Vinyl Carbenes via Site-Selective Vinylogous Mannich-Type Interception of Oxonium Ylides DOI

Rimei Zheng,

Aimin Xu,

Tianyuan Zhang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(29), P. 5509 - 5514

Published: July 13, 2023

A novel and highly stereoselective acyclic 1,3-difunctionalization of vinyl metal carbene species has been developed via Rh(II)/chiral phosphoric acid co-catalyzed three-component reactions vinyldiazoacetates with alcohols imines. This innovative approach features excellent regio-, diastereo-, enantioselectivities, demonstrating a broad scope functional group compatibility. Notably, this is the first example asymmetric in situ-formed carbenes.

Language: Английский

Citations

3
Carbene Formation or Reduction of the Diazo Functional Group? An Unexpected Solvent‐Dependent Reactivity of Cyclic Diazo Imides DOI Creative Commons
Yaseen Hussain, Claire Empel, René M. Koenigs

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(40)

Published: July 28, 2023

Abstract The control of the reactivity diazo compounds is commonly achieved by choice a suitable catalyst, e.g. via stabilization singlet carbenes or radical intermediates. Herein, we report on light‐promoted cyclic imides with thiols, where solvent results in two fundamentally different reaction pathways. In dichloromethane (DCM), carbene formed initially and engages cascade C−H functionalization/thiolation to deliver indane‐fused pyrrolidines good excellent yields. When switching acetonitrile solvent, pathway shut down an unusual reduction compound occurs under otherwise identical conditions, aryl thiol acts as reductant. A combined set experimental computational studies was carried out obtain mechanistic understanding support that indane formation proceeds insertion triplet carbene, while electron transfer process.

Language: Английский

Citations

2
Synthesis of 1H-Isoindole-Containing Scaffolds Enabled by a Nitrile Trifunctionalization DOI Creative Commons
Àlex Díaz‐Jiménez, Roger Monreal‐Corona, Miquel Solà

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 7381 - 7388

Published: April 26, 2024

Nitrogen ring structures are widely found in biologically active compounds and natural products, making their construction an important area of focus modern organic synthesis. In this work, the synthesis products containing 1H-isoindole motif has been successfully accomplished through a rhodium-catalyzed cascade, resulting significant increase molecular complexity. This reaction, which encompasses trifunctionalization nitrile moiety, is triggered by formation ylide with extended conjugation reaction rhodium vinylcarbene nitrile. The mechanism investigated means density functional theory calculations supported experimental data, enabling us to elucidate precise steps that explain rare trifunctionalization. A crucial step attack second azepine formed upon 1,7-electrocyclization conjugation.

Language: Английский

Citations

0
Rh(II)-Catalyzed Selective C(sp3)–H/C(sp2)–H Bonds Cascade Insertion to Construct [6–8–6] Benzo-Fused Scaffold DOI Creative Commons
T.X. Yu,

Feifei Fang,

Haowen Shou

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 10, 2024

The fused eight-membered carbocycles (EMCs) play vital roles in the medicinal and biological investigations of many natural products marketed drugs. traditional synthesis [6-8-6] benzo-fused derivatives involves multistep reactions low yields, making development a one-step method more challenging work. Here, we present novel strategy for construction scaffold from propargyl diazoacetates substituted with benzyl-nitrogen heterocyclic ring via Rh(ll)-catalyzed carbene/alkyne metathesis (CAM) selective C-H bond insertion. This exhibits specific substrate scope, simple operation, mild reaction conditions, high atom efficiency. Mechanistically, process sequential CAM, 1,3-H-shift, intramolecular nucleophilic attack, C(sp

Language: Английский

Citations

0