Steering Site‐Selectivity in Transition Metal‐Catalyzed C−H Bond Functionalization: the Challenge of Benzanilides DOI

Rafael Gramage‐Doria

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(44), P. 9688 - 9709

Published: April 1, 2020

Selective C-H bond functionalization catalyzed by metal complexes have completely revolutionized the way in which chemical synthesis is conceived nowadays. Typically, reactivity of a transition catalyst key to control site-, regio- and/or stereo-selectivity functionalization. Of particular interests are molecules that contain multiple bonds prone undergo activations with very similar dissociation energies at different positions. This case benzanilides, relevant motifs found many useful fine chemicals, two sites present chemically aromatic fragments. In last years, it has been depending on and reaction conditions, amide motif might behave as directing group towards metal-catalyzed activation benzamide site or anilide site. The impact consequences such subtle site-selectivity herein reviewed important applications carbon-carbon carbon-heteroatom forming processes. mechanisms unraveling these unique transformations discussed order provide better understanding for future developments field site-selective catalysts.

Language: Английский

Transition metal-catalyzed coupling of heterocyclic alkenesviaC–H functionalization: recent trends and applications DOI Open Access
Sundaravel Vivek Kumar, Sonbidya Banerjee, Tharmalingam Punniyamurthy

et al.

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(12), P. 1527 - 1569

Published: Jan. 1, 2020

Heterocyclic alkenes and their derivatives are an important class of reactive feedstock valuable synthons. This review highlights the transition-metal-catalyzed coupling heterocyclic alkenesviaa C–H functionalization strategy.

Language: Английский

Citations

84
Synthesis of Chiral Spirolactams via Sequential C−H Olefination/Asymmetric [4+1] Spirocyclization under a Simple CoII/Chiral Spiro Phosphoric Acid Binary System DOI
Wen‐Kui Yuan, Bing‐Feng Shi

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(43), P. 23187 - 23192

Published: Aug. 26, 2021

Abstract An unprecedented enantioselective synthesis of spiro‐γ‐lactams via a sequential C−H olefination/asymmetric [4+1] spirocyclization under simple Co II /chiral spiro phosphoric acid (SPA) binary system is reported. A range biologically important are obtained with high levels enantioselectivity (up to 98 % ee ). The concise, asymmetric an aldose reductase inhibitor was successfully achieved. Notably, contrast previous reports that relied on the use cyclopentadienyl or its derivatives (achiral Cp*, Cp tBu , chiral x ) ligated III complexes requiring tedious steps prepare, cheap and commercially available cobalt(II) acetate tetrahydrate used as efficient precatalyst.

Language: Английский

Citations

70
Recent advances in spirocyclization of maleimides via transition-metal catalyzed C–H activation DOI
Swadhin Swaraj Acharya,

Sagarika Patra,

Rojalini Maharana

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(15), P. 2916 - 2947

Published: Jan. 1, 2024

In recent years, the maleimide scaffold has received a great deal of attention in C–H activation.

Language: Английский

Citations

15
Weak Coordinating Carboxylate Directed Rhodium(III)-Catalyzed C–H Activation: Switchable Decarboxylative Heck-Type and [4 + 1] Annulation Reactions with Maleimides DOI
Mahadev Sharanappa Sherikar, Kandikere Ramaiah Prabhu

Organic Letters, Journal Year: 2019, Volume and Issue: 21(12), P. 4525 - 4530

Published: June 10, 2019

A weakly coordinating carboxylate directing group assisted C–H activation with maleimides leading to novel and switchable decarboxylative Heck-type [4 + 1] annulation products catalyzed by Rh(III) has been reported. In these reactions, solvents play a vital role in switching the selectivity. An aprotic solvent, THF, leads product while protic TFE, results product. The methodology shows high functional tolerance.

Language: Английский

Citations

63
Cobalt-Catalyzed Regioselective Direct C-4 Alkenylation of 3-Acetylindole with Michael Acceptors Using a Weakly Coordinating Functional Group DOI
Shyam Kumar Banjare, Tanmayee Nanda, Ponneri C. Ravikumar

et al.

Organic Letters, Journal Year: 2019, Volume and Issue: 21(19), P. 8138 - 8143

Published: Sept. 23, 2019

Herein, we disclosed the first report on selective C(4)–H functionalization of 3-acetylindole derivatives using first-row transition metal cobalt where an acetyl group is acting as a weakly coordinating directing group. Selective has been achieved diverse Michael acceptors (acrylate and maleimide) simply by switching additive from copper acetate to silver carbonate. Further formation cobaltacycle intermediate was also detected through HRMS for mechanistic insight.

Language: Английский

Citations

58
Transition Metal‐Catalysed Direct C−H Bond Functionalizations of 2‐Pyridone Beyond C3‐Selectivity DOI
Aniruddha Biswas, Saurabh Maity,

Subarna Pan

et al.

Chemistry - An Asian Journal, Journal Year: 2020, Volume and Issue: 15(14), P. 2092 - 2109

Published: June 5, 2020

2-Pyridone is a ubiquitous motif in natural products, drug molecules, ligands catalysis and organic materials. There necessity of direct step-economic methods for the construction 2-pyridone based molecules. Strategically, primary developments have led to C3-functionalizations due inherent reactivity this center. Despite this, many elegant transition metal-catalysed been established introduce versatile functional groups at C4, C5 C6-position via C-H bond functionalizations. This minireview focuses on categorized introduction different scaffolds beyond C3-selectivity discusses substrate scope, limitations plausible mechanistic details.

Language: Английский

Citations

53
Rhodium(III)-Catalyzed Dehydrogenative Annulation and Spirocyclization of 2-Arylindoles and 2-(1H-Pyrazol-1-yl)-1H-indoles with Maleimides: A Facile Access to Isogranulatimide Alkaloid Analogues DOI

Vikki N. Shinde,

Krishnan Rangan, Dalip Kumar

et al.

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(3), P. 2328 - 2338

Published: Jan. 12, 2021

A Rh(III)-catalyzed dehydrogenative annulation and spirocyclization of 2-arylindoles 2-(1H-pyrazol-1-yl)-1H-indole with maleimides is described. The cascade protocol provided highly functionalized benzo[a]pyrrolo[3,4-c]carbazole-1,3(2H,8H)-diones spiro[isoindolo[2,1-a]indole-6,3′-pyrrolidine]-2′,5′-diones in good to excellent. developed reaction methodology exhibited broad substrate scope functional group tolerance operationally simple scalable. Photophysical properties the annulated products were investigated. product showed high absorption emission values a large red-shift as compared that 2-phenylindole.

Language: Английский

Citations

44
Ru(II)-Catalyzed Switchable C–H Alkylation and Spirocyclization of 2-Arylquinoxalines with Maleimides via ortho-C–H Activation DOI

Sudip Laru,

Suvam Bhattacharjee,

Mukta Singsardar

et al.

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(3), P. 2784 - 2795

Published: Jan. 14, 2021

A Ru(II)-catalyzed facile and controllable protocol for C–H alkylation spirocyclization of 2-arylquinoxalines with maleimides has been achieved under ambient air in high yields. Sequential ortho-C–H activation C-annulation results the formation diverse polyheterocycles containing spiro[indeno[1,2-b]quinoxaline-11,3′-pyrrolidine]-2′,5′-diones, which are potent interest medicinal chemistry. Mechanistic investigations suggest a reversible cleavage bond turnover-limiting step.

Language: Английский

Citations

44
Diastereoselective palladium-catalyzed functionalization of prochiral C(sp3)–H bonds of aliphatic and alicyclic compounds DOI
Srinivasarao Arulananda Babu,

Yashika Aggarwal,

Pooja Patel

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(16), P. 2612 - 2633

Published: Jan. 1, 2022

Advancements in the palladium-catalyzed functionalization of diastereotopic or prochiral C(sp 3 )–H bonds generating stereogenic centers and stereo-arrays aliphatic compounds have been highlighted.

Language: Английский

Citations

33
Recent advances in transition-metal-catalyzed directed C–H alkenylation with maleimides DOI
Shuang‐Liang Liu, Changchun Ye, Xiaoge Wang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(24), P. 4837 - 4845

Published: Jan. 1, 2022

Transition-metal-catalyzed directed C-H alkenylation with maleimides has attracted much attention in recent years, as maleimide core moieties are present various natural products and pharmaceuticals. In addition, these derivatives can be readily modified into biologically important compounds including succinimides, pyrrolidines γ-lactams. The efficient chelation-assisted inert bond activation strategy provides straightforward access to a wide array of structurally diverse molecules containing units. This review describes the major progress mechanistic investigations on Heck-type reaction/cyclization organic until early 2022.

Language: Английский

Citations

32