Silver-Promoted Three-Component Synthesis of Perfluoroalkenyl Pyrroles through Partial Defluorinative Functionalization of Perfluoroalkyl Halides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6197 - 6202

Published: July 15, 2024

A silver-promoted three-component heterocyclization of alkynes, perfluoroalkyl halides, and 1,3-dinucleophiles was developed for the efficient synthesis privileged (E)-perfluoroalkenyl pyrroles. The reaction proceeded through a rationally designed sequence radical perfluoroalkylation intramolecular defluorinative [3 + 2]-heterocyclization. utility halide as perfluoroalkenyl reagent, by selective controllable functionalization two inert C(sp3)–F bonds at vicinal carbon centers on chain, provides new mode value-added organofluorides starting from easily available low-cost fluorinated feedstock.

Language: Английский

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Defluorinative Cyclization of Enamides with Fluoroalkyl Halides Through Two Vicinal C(sp³)─F Bonds Functionalization

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 31, 2024

Abstract Introducing distinctive functional groups to expand the structural diversity and improve intrinsic properties of parent molecules has been an essential pursuit in organic chemistry. By using perfluoroalkyl halide (PFAH) as a nontraditional, readily available, ideal 1,2‐difluoroalkenyl coupling partner, defluorinative cyclization reaction enamides for construction fluoroalkenyl oxazoles is first developed. The selective controllable two‐fold cleavage vicinal C(sp 3 )─F bonds PFAH not only enables introduction specific moiety with ease but also results functionalization two 2 )─H without need metal catalyst, photocatalyst, oxidant, or light. method can be applied late‐stage modification complex molecules, synthesis biological‐relevant oxazole analoges, scale‐up synthesis, which all further highlight real‐world utility this protocol. Mechanistic studies reveal that possibly proceeds through radical perfluoroalkylation, consecutive C─F bond heterolytic cleavage, process. In addition, situ formed may serve hydrogen abstractor.

Language: Английский

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Photoredox‐Enabled Manganese‐Catalyzed [2+2+2] Cycloaddition of Alkynes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1545 - 1550

Published: Feb. 8, 2024

Abstract Manganese (Mn) is the third most abundant transition metal on Earth and known for its exceptional biocompatibility. The development of novel catalytic mode Mn great significance to advancing organic synthesis. In this study, first manganese (Mn)‐catalyzed [2+2+2] cycloaddition alkynes achieved with aid visible‐light photoredox catalysis. Photoredox catalysis proposed promote transformation by in situ reduction high‐valent Mn(II) complex Mn(0) species, thereby initiating reaction. Additionally, a photooxidation‐induced reductive ellimination step also suggested. This system further distinguished notable tolerance towards both terminal internal as counterparts diynes.

Language: Английский

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Pd-Catalyzed Difluoroalkylation of Alkenes Using Chlorodifluoroalkanes

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 18499 - 18506

Published: Dec. 4, 2024

Language: Английский

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Photoinduced radical cyclization reaction of isocyanides with α-carbonyl bromides to access 11-alkyl-substituted 1,4-dibenzodiazepines

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A photochemical radical cascade cyclization reaction of isocyanides with α-carbonyl bromides under mild conditions is disclosed for accessing 1,4-dibenzodiazepines, demonstrating good tolerance towards various functional groups.

Language: Английский

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Monodefluorinative Halogenation of Perfluoroalkyl Ketones via Organophosphorus-Mediated Selective C–F Activation

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Through the prosperity of organofluorine chemistry in modern organic synthesis, perfluorinated compounds are now abundant and widely available. Consequently, these substances become attractive starting materials for production complex, multifunctional fluorinated molecules. However, inherent challenges associated with activation discrimination C–F bonds typically lead to overdefluorination as well functional group incompatibility. To address problems, our utilized a rationally designed organophosphorus reagent that promoted mild selective manipulation single bond trifluoromethyl pentafluoroethyl ketones via an interrupted Perkow-type reaction, which allowed replacement fluorine more labile synthetically versatile congeners such chlorine, bromine, iodine. The resulting α-haloperfluoroketones have two reactive units orthogonal properties would be suitable subsequent structural diversification. DFT calculations identified favorable P–F interaction crucial factor from both thermodynamic kinetic viewpoints.

Language: Английский

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Near-Infrared-Light-Induced Iron(I) Dimer Enabled Abstraction of Ester Group from Cycloketone Oxime Esters

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

Photoinduced dimeric metal complexes have been extensively utilized in halogen atom transfer (XAT) reactions. In this study, we successfully achieved the abstraction of ester group from cyclobutanone oxime esters via iron(I)-dimer catalysis under near-infrared (NIR) light (730 nm) excitation, enabling efficient synthesis cyanoalkylated alkenes, quinazolinones, and 3,3-disubstituted oxindoles. Mechanistic investigations confirmed NIR-induced functional process.

Language: Английский

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Photoinduced Cobalt-Catalyzed Carbonyl Umpolung Alkenylation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 15, 2025

Herein we introduce a cobalt-catalyzed umpolung strategy for radical carbonyl alkenylation. This method provides an alternative pathway producing Grignard-type products from (hetero)aryl vinyl bromides and aliphatic aldehydes without pre-functionalization. The is distinguished by its broad substrate scope, mild reaction conditions, simple catalytic system. Upon specific activation of the group with AcI, cobaloxime complex catalyst facilitates selective reduction resulting α-oxy iodide through atom transfer process.

Language: Английский

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Photocatalytic synthesis of polyfluoroalkylated dihydropyrazoles and tetrahydropyridazines

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(77), P. 10764 - 10767

Published: Jan. 1, 2024

A photocatalytic trifluoromethylation/cyclization reaction of

Language: Английский

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Manganese(I)‐Catalyzed Enantioselective C(sp²)−C(sp³) Bond‐Forming for the Synthesis of Skipped Dienes with Synergistic Aminocatalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 16, 2024

Abstract Mn(I)‐catalyzed enantioselective C−C bond‐forming reactions represent a great challenge in homogeneous catalysis primarily due to limited understanding of its mechanistic principles. Herein, we have developed an interesting catalytic strategy that leverages synergistic combination dimeric manganese(I) catalyst and chiral aminocatalyst address this issue. A range conjugated dienals trienals can exclusively proceed 1,4‐hydroalkenylation by using readily available aromatic aliphatic alkenyl boronic acids as coupling partners, producing rich library skipped diene aldehydes synthetically useful yields high levels enantioselectivities. Notably, downstream transformations these products not only afford concise approach construct enantioenriched trienes but also realize total synthesis analogues (−)‐Blepharocalyxin D four steps. DFT calculations suggest the is kinetically more favorable than 1,6‐hydroalkenylation.

Language: Английский

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