Domino C–H Activation/Directing Group Migration/Alkyne Annulation: Unique Selectivity by d⁶-Cobalt(III) Catalysts

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(7), P. 4444 - 4450

Published: March 16, 2020

Distinct selectivity control in Cp*CoIII-catalyzed domino C–H activation/pyridine directing group migration/alkyne annulation has been accomplished through the nucleophilicity of an organometallic cobalt intermediate with a d6 electron configuration. Detailed mechanistic studies provided compelling evidence for facile activation along favorable migration Cp*CoIII catalysis, rather than β-oxygen elimination observed (CO)3MnI manifold.

Language: Английский

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Transition Metal‐Catalysed Direct C−H Bond Functionalizations of 2‐Pyridone Beyond C3‐Selectivity

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

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Sequential C–H and C–C Bond Cleavage: Divergent Constructions of Fused N-Heterocycles via Tunable Cascade

ACS Catalysis, Journal Year: 2019, Volume and Issue: 9(9), P. 8749 - 8756

Published: Aug. 22, 2019

Streamlining the generation of diverse highly functionalized molecules from abundant feedstocks holds great synthetic promises and challenges in pharmaceutical material discovery. Herein, we report a tunable selectivity multiple cascade reactions for divergent assembly fused N-heterocycles, comprising sequential activation C–H C–C bonds. Isolatable indene-type intermediates might be responsible densely substituted pyridines, azepines, azafluorenones products. The tolerance strongly coordinating those readily applicable late-stage modifications pharmaceuticals precursors, further demonstrated robustness this transformation.

Language: Английский

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A Highly Efficient Dimeric Manganese‐Catalyzed Selective Hydroarylation of Internal Alkynes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(31), P. 12789 - 12794

Published: April 24, 2020

We have developed a general and site-predictable manganese-catalyzed hydroarylation of internal alkynes in the presence water, under an air atmosphere without involvement ligand. The unique catalytic feature this reaction is highlighted by comparison with other widely used transition metal catalysts including palladium, rhodium, nickel, or copper. simple operation, high efficiency excellent functional group compatibility make protocol practical for more than 90 structurally diverse alkynes, overcoming influence both electronic steric effect alkynes. Its exclusive regio- chemoselectivity originates from reactivity manganese-based catalyst towards inherent double controlled strategy sterically hindered propargyl alcohols installing external directing groups. synthetic robustness practicality been illustrated concise synthesis bervastatin, hypolipidemic drug, late-stage modification complex precise regioselectivity.

Language: Английский

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Rhodium(III)-catalyzed [4 + 2] annulation of N-arylbenzamidines with 1,4,2-dioxazol-5-ones: Easy access to 4-aminoquinazolines via highly selective C H bond activation

Chinese Chemical Letters, Journal Year: 2021, Volume and Issue: 32(8), P. 2592 - 2596

Published: Feb. 27, 2021

Language: Английский

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Co(III)-Catalyzed Regioselective Benzannulation of Substituted Pyridones with 1,6-Diynes via Dual C-H Bond Activation

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(63), P. 8296 - 8299

Published: Jan. 1, 2024

A Co(III)-catalyzed site-selective C5 and C6 benzannulation of substituted pyridones with 1,6-diynes

Language: Английский

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Merging C–H Vinylation with Switchable 6π-Electrocyclizations for Divergent Heterocycle Synthesis

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(36), P. 15585 - 15594

Published: Aug. 12, 2020

Pyridinium-containing polyheterocycles exhibit distinctive biological properties and interesting electrochemical optical thus are widely used as drugs, functional materials, photocatalysts. Here, we describe a unified two-step strategy by merging Rh-catalyzed C–H vinylation with two switchable electrocyclizations, including aza-6π-electrocyclization all-carbon-6π-electrocyclization, for rapid divergent access to dihydropyridoisoquinoliniums dihydrobenzoquinolines. Through computation, the high selectivity of aza-electrocyclization in presence an appropriate "HCl" source under either thermal conditions or photochemical is shown result from favorable kinetics symmetries frontier orbitals. We further demonstrated value this protocol synthesis several complex pyridinium-containing polyheterocycles, alkaloids berberine chelerythrine.

Language: Английский

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Recent advances on non-precious metal-catalyzed C–H functionalization of N-heteroarenes

Chemical Communications, Journal Year: 2021, Volume and Issue: 58(1), P. 10 - 28

Published: Nov. 18, 2021

N-Heteroarenes are widely used for numerous medicinal applications, lifesaving drugs and show utmost importance as intermediates in chemical synthesis. This feature article highlights the recent advances, from 2015 to August 2021, on sp2 sp3 C-H bond functionalization reactions of various N-heteroarenes catalyzed by non-precious transition metals (Mn, Co, Fe, Ni, etc.). The salient features report are: (i) development newer catalysis Csp2-H activation categorized into alkylation, alkenylation, borylation, cyanation, annulation reactions, (ii) advances Csp3-H considering approaches alkylation well alkenylation processes, (iii) synthetic applications practical utility catalytic protocols utilized late-stage drug development; (iv) scope along with mechanistic studies detail findings important processes.

Language: Английский

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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, Journal Year: 2021, Volume and Issue: 2021(15), P. 2223 - 2229

Published: April 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.

Language: Английский

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Recyclable rhodium-catalyzed C–H activation/[4 + 2] annulation with unconventional regioselectivity at ambient temperature: experimental development and mechanistic insight

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(18), P. 7012 - 7021

Published: Jan. 1, 2022

A robust and convenient rhodium-catalyzed unconventionally regioselective C–H activation/[4 + 2] annulation for the synthesis of isoquinolones which are prevalent in natural products pharmaceuticals was developed.

Language: Английский

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