Recent Advances in Cyclization Reactions of 1,6‐Enynes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(6), P. 1220 - 1268

Published: Jan. 22, 2024

Abstract Elaborated molecular architectures, specifically those bearing one or more carbon stereocenters, stand as an important class of carbocyclic and heterocyclic frameworks because they are frequently occurring core structures in numerous natural products biologically active pharmaceutical molecules. Over the past few decades, development versatile synthetic approaches via cascade cyclization reactions 1,6‐enynes for construction a series fused spiro compounds has been focus great deal research initiatives. These synthesis strategies peculiarly fascinating context assembly wide array molecules, products, agrochemicals, functional materials. In this review, recent developments transformations with diverse coupling reagents summarized since 2018, which could be divided into five categories: 1) Introduction; 2) Transition metal catalyzed 1,6‐enynes; 3) Metal‐free 4) Visible‐light‐induced 5) Electrocatalytic 1,6‐enynes.

Language: Английский

---

Rhodium(III)‐Catalyzed Regioselective C−H Annulation and Alkenylation of 2‐Pyridones with Terminal Alkynes

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(7), P. 1264 - 1270

Published: Feb. 19, 2022

Abstract Cp*Rh(III)‐catalyzed regioselective C−H annulation and alkenylation of 2‐pyridones with terminal alkynes have been developed. The cationic Cp*Rh(III) catalytic system containing FeCl 3 additive enables 1‐(2‐pyridyl)‐2‐pyridones alkynes, providing efficient access to 5,7‐diarylated 2‐quinolinones. reaction pathway can be switched [Cp*RhCl 2 ] as the catalyst, NaOAc HOAc solvent, affording C6‐alkenylated in high yields. These protocols accommodate a wide range substrates good functional group compatibility. magnified image

Language: Английский

---

Robust Synthesis of Terpenoid Scaffolds under Mn(I)-Catalysis

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(15), P. 10761 - 10771

Published: July 18, 2023

The 6/6/5-fused tricyclic scaffold is a central feature of structurally complex terpenoid natural products. A step-economical cascade transformation that leads to molecular skeleton regarded as sustainable methodology. Therefore, we report the first Mn(I)-catalyzed C(sp2)-H chemoselective in situ dienylation and diastereoselective intramolecular Diels-Alder reaction using iso-pentadienyl carbonate access scaffolds. To best our knowledge, there no such thus far utilize substrate C-H activation catalysis. Extensive mechanistic studies, isolation catalytically active organo-manganese(I) complexes, 1,3-dienyl-intermediates, isotopic labeling experiments have supported proposed mechanism this reaction.

Language: Английский

---

Chemical insights into the synthetic chemistry of five-membered saturated heterocycles—a transition metal–catalyzed approach

Frontiers in Chemistry, Journal Year: 2023, Volume and Issue: 11

Published: July 26, 2023

Drug design and delivery is primarily based on the hunt for new potent drug candidates novel synthetic techniques. Recently, saturated heterocycles have gained enormous attention in medicinal chemistry as evidenced by drugs listed FDA Orange Book. Therefore, demand heterocyclic syntheses has increased tremendously. Transition metal (TM)–catalyzed reactions remained prime priority last three decades. Nowadays, TM catalysis well adorned combining it with other techniques such bio- and/or enzyme-catalyzed reactions, organocatalysis, or using two different metals a single catalysis. This review highlights recent developments of transition metal–catalyzed synthesis five-membered heterocycles.

Language: Английский

---

Thiourea‐Promoted Cascade Dihalogenation‐Cyclization of Cyclohexadienone‐Containing 1,6‐Enynes

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(4), P. 482 - 489

Published: Jan. 19, 2023

Abstract Organohalogens play an important role in the drug discovery and functional materials. However, convenient preparation of organohalogens still remains a challenging task. Herein, we report metal‐free cascade dihalogenation‐cyclization cyclohexadienone‐containing 1,6‐enynes biodegradable solvent to generate dibrominated cis ‐tetrahydrobenzofuran‐5(4 H )‐ones ‐dihydrobenzopyran‐6(5 respectively bearing 1,4‐dibromobut‐1‐enyl subunit trans‐trans trans‐cis form. A subgram‐scale experiment several downstream transformations are presented for elaborating synthetic utility. Moreover, potent anticancer activity is observed against MDA‐MB‐468 cells corresponding products. magnified image

Language: Английский

---