Transition metal-catalyzed C–H/C–C activation and coupling with 1,3-diyne

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(14), С. 2842 - 2869

Опубликована: Янв. 1, 2023

The 1,3-diynes hold a prominent position among the many coupling partners employed in metal-catalysed C–H activation because of their ability to form complex bis-heterocycles one shot.

Язык: Английский

---

Ir(III)-Catalyzed Dual C–H Activation of 2-Aryl Phthalazinediones and 3-Aryl-2H-benzo[e][1,2,4]thiadiazine-1,1-dioxides for the Construction of Spiro-Fused Cyclic Frameworks

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(5), С. 2758 - 2772

Опубликована: Фев. 21, 2023

An Ir(III)-catalyzed double C–H activation strategy has been developed for the synthesis of highly rigid spiro frameworks by means ortho-functionalization 2-aryl phthalazinediones and 2,3-diphenylcycloprop-2-en-1-ones using Ir(III)/AgSbF6 catalytic system. Similarly, 3-aryl-2H-benzo[e][1,2,4]thiadiazine-1,1-dioxides undergo smooth cyclization with to afford a diverse range compounds in good yields excellent selectivity. Additionally, 2-arylindazoles provide corresponding chalcone derivatives under similar reaction conditions.

Язык: Английский

---

Rh(III)‐Catalyzed [3+2] Annulation and C−H Alkenylation of Indoles with 1,3‐Diynes by C−H Activation

European Journal of Organic Chemistry, Год журнала: 2021, Номер 2021(15), С. 2223 - 2229

Опубликована: Апрель 12, 2021

Abstract Described herein is the Rh(III)‐ catalyzed [3+2] annulations and C2‐alkenylations of indoles with 1,3‐diynes, which deliver synthetically important 3 H ‐pyrrolo[1,2‐ a ]indol‐3‐ones highly functionalized tetrasubstituted olefin derivatives. Importantly, in this methodology, additive controlled selective formation desired scaffolds. This synthetic strategy exhibits high efficiency broad functional group compatibility. Furthermore, protocol has been successfully extended to synthesis bis‐annulated trisubstituted alkenes. The method also smoothly applied for core structure protein kinase C inhibitor melatonin analogues.

Язык: Английский

---

Chemo-, Regio-, and Stereoselective Assembly of Polysubstituted Furan-2(5H)-ones Enabled by Rh(III)-Catalyzed Domino C–H Alkenylation/Directing Group Migration/Lactonization: A Combined Experimental and Computational Study

ACS Catalysis, Год журнала: 2021, Номер 11(22), С. 13921 - 13934

Опубликована: Ноя. 2, 2021

Exploring multistep cascade reactions triggered by C–H activation are recognized as appealing, yet challenging. Herein, we disclose a Rh(III)-catalyzed domino coupling of N-carbamoyl indoles and 4-hydroxy-2-alkynoates for the streamlined assembly highly functionalized furan-2(5H)-ones in which carbamoyl-directing group (DG) is given dual role an auxiliary migrating acylating reagent via cleavage stable C–N bonds at room temperature. More importantly, obtained furan-2(5H)-one skeleton could be further under air situ C5–H hydroxylation simply switching solvent or additive, providing fully substituted with installation alcohol-based C5 quaternary carbon center. Detailed experimental studies density functional theory calculations reveal that Rh(III)-mediated tandem activation/alkyne insertion/DG migration/lactonization accounts developed transformation to achieve high functionalities observed exclusive selectivity. The potential biological application class potent PPARγ ligands highlights synthetic utility methodology. This protocol endowed several salient features including efficient activation, excellent chemo-, regio-, stereoselectivity, bond-forming efficiency (e.g., two C–C C–O bonds), solvent- additive-controlled product selectivity, good functional-group compatibility, mild redox-neutral conditions.

Язык: Английский

---

Rhodium(iii)-catalyzed regioselective C2-alkenylation of indoles with CF₃-imidoyl sulfoxonium ylides to give multi-functionalized enamines using a migratable directing group

Chemical Communications, Год журнала: 2022, Номер 59(3), С. 318 - 321

Опубликована: Дек. 7, 2022

A rhodium(III)-catalyzed regioselective C2-alkenylation of indoles for the construction α-CF3 substituted enamines has been developed, which utilizes CF3-imidoyl sulfoxonium ylides (TFISYs) as alkenylating agents first time. wide array indolyl- and trifluoromethyl-decorated enamine derivatives have assembled in moderate to good yields.

Язык: Английский

---

Rh(III)-Catalyzed Selective Olefination of N-Carboxamide Indoles with Unactivated Olefins at Room Temperature via an Internal Oxidation

Organic Letters, Год журнала: 2022, Номер 24(5), С. 1121 - 1126

Опубликована: Янв. 31, 2022

A mild, convenient, and effective Rh(III)-catalyzed site-selective C2-alkenylation of N-carboxamide indoles with unactivated alkenes at room temperature via an internal oxidation is described. The present olefination reaction was well-studied plentiful indole N-carboxamides as well unfunctionalized/functionalized alkenes. In this reaction, the directing group containing N-OMe acts oxidant. possible mechanism involving C-H activation/insertion/internal followed by protonation proposed supported deuterium-labeling studies.

Язык: Английский

---

[RhCp*Cl₂]₂-Catalyzed Indole Functionalization: Synthesis of Bioinspired Indole-Fused Polycycles

ACS Omega, Год журнала: 2023, Номер 8(31), С. 27894 - 27919

Опубликована: Июль 25, 2023

Polycyclic fused indoles are ubiquitous in natural products and pharmaceuticals due to their immense structural diversity biological inference, making them suitable for charting broader chemical space. Indole-based polycycles continue be fascinating as well challenging targets synthetic fabrication because of characteristic frameworks possessing biologically intriguing compounds both origin. As a result, an assortment new processes catalytic routes has been established provide unified access these skeletons very efficient selective manner. Transition-metal-catalyzed processes, particular from rhodium(III), widely used endeavors increase molecular complexity efficiently. In recent years, this resulted significant progress reaching scaffolds with enormous activity based on core indole skeletons. Additionally, Rh(III)-catalyzed direct C–H functionalization benzannulation protocols moieties were one the most alluring techniques generate indole-fused polycyclic molecules This review sheds light developments toward synthesizing by cascade annulation methods using Rh(III)-[RhCp*Cl2]2-catalyzed pathways, which align comprehensive sophisticated field functionalization. Here, we looked at few cascade-based designs catalyzed Rh(III) that produced elaborate inspired bioactivity. The also strongly emphasizes mechanistic insights 1–2, 2–3, 3–4-fused systems, focusing routes. With emphasis efficiency product diversity, chosen carbocycles heterocycles least three fused, bridged, or spiro cages reviewed. newly created synthesis concepts toolkits accessing diazepine, indol-ones, carbazoles, benzo-indoles, illustrative privileged techniques, included featured collection.

Язык: Английский

---

Rhodium‐Catalyzed Atroposelective Access to Axially Chiral Olefins via C−H Bond Activation and Directing Group Migration

Angewandte Chemie, Год журнала: 2021, Номер 134(1)

Опубликована: Окт. 22, 2021

Abstract Axially chiral open‐chain olefins represent an underexplored class of platform. In this report, two classes tetrasubstituted axially acyclic have been accessed in excellent enantioselectivity and regioselectivity via C−H activation (hetero)arenes assisted by a migratable directing group en route to coupling with sterically hindered alkynes. The indoles bearing N‐aminocarbonyl afforded C–N acrylamides the assistance racemic zinc carboxylate additive. DFT studies suggest β‐nitrogen elimination–reinsertion pathway for migration. Meanwhile, employment N‐phenoxycarboxamide delivered C−C enamides migration oxidizing group. Experiments that both cases (hetero)arene substrate adopts well‐defined orientation during activation, which turn determines disposition alkyne migratory insertion. Synthetic applications representative are demonstrated.

Язык: Английский

---

Palladium(II)-Catalyzed Intramolecular [2 + 2 + 2] Annulation of Indolyl 1,3-Diynes: Construction of Azepino-Fused Carbazoles

Organic Letters, Год журнала: 2023, Номер 25(25), С. 4615 - 4620

Опубликована: Июнь 21, 2023

A novel palladium(II)-catalyzed intramolecular [2 + 2 2] annulation of indolyl 1,3-diynes is described in this contribution. variety azepino-fused carbazoles are obtained moderate to excellent yields. The key the success transformation use a carboxylic acid as an additive. This protocol features broad functional group tolerances, easy handling air, and 100% atom economy. Furthermore, scale-up reactions, late-stage derivatizations, photophysical property investigations highlight potential synthetic utility methodology.

Язык: Английский

---

Co(iii)-Catalyzed three-component assembling of N-(2-pyrimidyl) indoles with dienes and formaldehyde

Chemical Communications, Год журнала: 2023, Номер 59(47), С. 7216 - 7219

Опубликована: Янв. 1, 2023

A highly regio- and chemoselective three-component assembling of N-pyrimidyl indoles with dienes formaldehyde in the presence a Co(III) catalyst was demonstrated. The scope reaction investigated variety indole derivatives to synthesize substituted homoallylic alcohols. Both butadiene isoprene units were compatible reaction. To understand mechanism, various investigations carried out, suggested plausibility mechanism involving C-H bond activation as key step.

Язык: Английский

---