Recent advances in three-component difunctionalization ofgem-difluoroalkenes

Chemical Communications, Год журнала: 2020, Номер 56(72), С. 10442 - 10452

Опубликована: Янв. 1, 2020

Three-component difunctionalization ofgem-difluoroalkenesviathe generation and transformation of a α-fluoroalkylated carbanion, carbon–metal species, radical, carbocation intermediate.

Язык: Английский

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Synthesis of Monofluoroalkenes: A Leap Forward

Synthesis, Год журнала: 2018, Номер 50(05), С. 881 - 955

Опубликована: Янв. 11, 2018

Monofluoroalkenes have found wide application in organic chemistry, medicinal and materials science. This review summarizes the most recent advances made regarding preparation of monofluoroalkenes, covering period between October 2010 September 2017. is divided three main parts, one for each possible substitution pattern, namely di-, tri-, tetrasubstituted. Then, class, further subclassification according to reaction type. 1 Introduction 2 Disubstituted 2.1 α-Monofluoroalkenes 2.2 β-Monofluoroalkenes 3 Trisubstituted 4 Tetrasubstituted 5 Conclusions

Язык: Английский

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Modern strategies for C–H functionalization of heteroarenes with alternative coupling partners

Chem, Год журнала: 2021, Номер 7(10), С. 2585 - 2634

Опубликована: Авг. 27, 2021

Язык: Английский

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Cobalt-catalyzed C–H activation: recent progress in heterocyclic chemistry

Catalysis Science & Technology, Год журнала: 2018, Номер 8(23), С. 5983 - 6018

Опубликована: Янв. 1, 2018

Cobalt-catalyzed C–H activation has gone through some major advancements in the past couple of decades.

Язык: Английский

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Visible Light‐Mediated Trifluoromethylation of Fluorinated Alkenes via C−F Bond Cleavage

Advanced Synthesis & Catalysis, Год журнала: 2018, Номер 360(20), С. 3894 - 3899

Опубликована: Авг. 9, 2018

Abstract A convenient photoredox‐catalyzed defluorinative trifluoromethylation of α ‐trifluoromethyl alkenes and gem ‐difluoroalkenes is developed. The reactions proceeded efficiently via trifluoromethyl radical addition followed by β ‐fluorine elimination process, providing a new entry to multifluorinated in moderate good yields with excellent stereoselectivity. magnified image

Язык: Английский

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Reactivity-Controlling Factors in Carboxylate-Assisted C–H Activation under 4d and 3d Transition Metal Catalysis

ACS Catalysis, Год журнала: 2020, Номер 10(18), С. 10551 - 10558

Опубликована: Авг. 17, 2020

Detailed density functional theory calculations provide valuable insight into reactivity-controlling factors in transition metal-catalyzed C–H activation by carboxylate assistance. The chelation-assisted of a variety arenes 3d and 4d metal complexes was analyzed means bond order analysis through (DFT) as well energy decomposition DLPNO–CCSD(T) calculations, thereby providing in-depth information on distinct electronic influences the key state demonstrating preferred base-assisted internal electrophilic substitution (BIES) rather than concerted metalation-deprotonation (CMD) pathway.

Язык: Английский

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Stereoselective Palladium‐Catalyzed C−F Bond Alkynylation of Tetrasubstituted gem‐Difluoroalkenes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(28), С. 11293 - 11297

Опубликована: Апрель 18, 2020

A stereoselective Pd(PPh3 )4 -catalyzed C-F bond alkynylation of tetrasubstituted gem-difluoroalkenes with terminal alkynes has been developed. This method gives access to a great variety conjugated monofluoroenynes bearing alkene moiety well-defined stereochemistry. Chelation-assisted oxidative addition Pd the is proposed account for high level stereocontrol. An X-ray crystal structure key monofluorovinyl PdII intermediate obtained first time as evidence mechanism.

Язык: Английский

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C−H Functionalization of Indoles by 3d Transition‐Metal Catalysis

Asian Journal of Organic Chemistry, Год журнала: 2019, Номер 9(3), С. 326 - 342

Опубликована: Окт. 29, 2019

Abstract Over the past decade, use of 3d transition metal for regioselective C−H bond functionalization indoles has significantly increased. Particularly, advances in manganese, iron, cobalt, nickel and copper catalysis have demonstrated selective C(2)−H C(3)−H arylation, alkenylation, alkynylation alkylation to a greater extent. Similarly, C−O C−N bond‐forming reactions are manifested via direct activation by these earth‐abundant metals. The emergence metals biologically relevant related heteroarenes would make this protocol more attractive practical applications. Herein, we provide brief overview metal‐catalyzed (mostly Mn, Fe, Co, Ni Cu) heteroarenes.

Язык: Английский

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gem ‐Difluoromethylene Alkyne‐Enabled Diverse C−H Functionalization and Application to the on‐DNA Synthesis of Difluorinated Isocoumarins

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(4), С. 1959 - 1966

Опубликована: Окт. 6, 2020

Using gem-difluoromethylene alkynes as effectors, unprecedented diverse C-H activation/[4+2] annulations of simple benzoic acids are reported. The chemodivergent reaction outcomes well-tuned by Rh/Ir-catalyzed system; in the RhIII catalysis, 3-alkenyl-1H-isochromen-1-one and 3,4-dialkylideneisochroman-1-one skeletons afforded a solvent-dependent manner whereas difluoromethylene-substituted 1H-isochromen-1-ones generated under IrIII -catalyzed system. Mechanistic studies revealed that unusually double β-F eliminations fluorine effect-induced regioselective reductive elimination independently involved to enable distinct modes for divergent product formations. Besides, synthetic application both derivatization obtained diene products on-DNA synthesis DNA-tagged difluorinated isocoumarin have been demonstrated, which manifested great potential utility developed protocols.

Язык: Английский

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Rhodium(iii)-catalyzed regio- and stereoselective benzylic α-fluoroalkenylation with gem-difluorostyrenes

Chemical Communications, Год журнала: 2017, Номер 53(74), С. 10326 - 10329

Опубликована: Янв. 1, 2017

Rhodium(iii)-catalyzed mild benzylic α-fluoroalkenylation of 8-methylquinolines with gem-difluorostyrenes has been developed. This reaction occurred via C-H activation and C-F cleavage is applicable to a wide range substrates, leading the synthesis Z-alkenyl fluorides under redox-neutral conditions high regio- stereoselectivity.

Язык: Английский

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