Nickel-catalyzed direct C-H trifluoroethylation of heteroarenes with trifluoroethyl iodide.

  title={Nickel-catalyzed direct C-H trifluoroethylation of heteroarenes with trifluoroethyl iodide.},
  author={Shengyi Yan and Zhuo-Zhuo Zhang and Bing‐Feng Shi},
  journal={Chemical communications},
  volume={53 74},
A highly selective nickel-catalyzed C-H trifluoroethylation of heteroarenes was developed with the assistance of a monodentate directing group. This protocol provides efficient access to various trifluoroethyl-substituted heteroarenes, including indoles, pyrroles, furans, and thiophenes, with commercially available CF3CH2I as an alkylation reagent. This robust catalytic procedure is scalable and tolerates a broad range of functional groups. Moreover, multifluoroalkylation of indoles is also… 
Ligand- and Additive-Free 2-Position-Selective Trifluoromethylation of Heteroarenes Under Ambient Conditions
This protocol provides an easy and rapid method to various 2-position-selective trifluoromethylated heteroarenes including indoles, pyrroles, benzofuran, and acetanilide.
Rhodium(iii)-catalyzed CF3-carbenoid C-H functionalization of 6-arylpurines.
An efficient method for the CF3-carbenoid C-H functionalization of 6-arylpurines has been developed that provides the corresponding carbene insertion products with high regioselectivity within a few hours and allow the introduction of both theCF3 and carboxylate functions into biologically important purine molecules including nucleoside derivatives.
Nickel-Catalyzed Regioselective C(2)-H Difluoroalkylation of Indoles with Difluoroalkyl Bromides.
Synthetic utility of this nickel-catalyzed method is demonstrated by synthesizing melatonin receptor antagonist Luzindole derivative and shows excellent regioselectivity and exhibits a broad substrate scope.
The copper(ii)-catalyzed and oxidant-promoted regioselective C-2 difluoromethylation of indoles and pyrroles.
Generally, this C-2 difluoromethylation of bioactive molecules containing an indole ring was achieved in good yields and features excellent functional group compatibility, broad substrate scope and excellent C- 2 selectivity.
Photo-Induced Cross-Dehydrogenative Alkylation of Heteroarenes with Alkanes under Aerobic Conditions.
A Minisci-type cross-dehydrogenative alkylation in an aerobic atmosphere using abundant and inexpensive cerium chloride as a photocatalyst and air as an oxidant is reported, generating the corresponding products in moderate-to-good yields.
Nickel‐Catalyzed C−H Bond Functionalization of Azoles and Indoles
This Account summarizes the developments in nickel‐catalyzed regioselective functionalization of azoles and indoles with a considerable focus on the reaction mechanism.
Copper-catalyzed one-pot synthesis of 2-(2,2,2-trifluoroethyl)-substituted benzofused heterocycles
A method for copper-catalyzed synthesis of 2-trifluoroethyl-substituted benzofurans and indoles from the reaction of salicylaldehyde/2-aminobenzaldehyde p-tosylhydrazones with
Elemental sulfur-promoted one-pot synthesis of 2-(2,2,2-trifluoroethyl)benzoxazoles and their derivatives.
The scope of this methodology was further extended to the synthesis of the trifluoroethylated benzothiazole and benzoimidazole derivatives and a plausible mechanism was proposed on the basis of isolation and characterization of a thioamide intermediate.
Tri- and di-fluoroethylation of alkenes by visible light photoredox catalysis
The tri- and di-fluoroethylation of alkenes with sulfonium salts, (Ph2S+CH2RF TfO−) (RF = CF3 or HCF2), by visible light photoredox catalysis to give tri-/di-fluoroethyl alkenes or
Denitrogenative Hydrotrifluoromethylation of Benzaldehyde Hydrazones: Synthesis of (2,2,2-Trifluoroethyl)arenes.
This novel reaction was tolerant to a large number of electronically-diverse functional groups and substitution patterns, as well as naphthyl- and heteroaryl-derived substrates, and being transition metal-free.


Palladium-catalyzed cascade C-H trifluoroethylation of aryl iodides and Heck reaction: efficient synthesis of ortho-trifluoroethylstyrenes.
A palladium-catalyzed selective C-H bond trifluoroethylation of aryl iodides has been explored, and preliminary mechanistic studies indicate that the reaction might involve a key Pd(IV) intermediate, generated through the rate-determining oxidative addition of CF3CH2I to a palladacycle.
Alkylations of Arylboronic Acids including Difluoroethylation/Trifluoroethylation via Nickel‐Catalyzed Suzuki Cross‐Coupling Reaction
An efficient alkylation method of functionalized alkyl halides under mild nickel-catalyzed C(sp3)C(sp2) Suzuki cross-coupling conditions is described. The features of this approach are excellent
Nickel-Catalyzed Ortho-Arylation of Unactivated (Hetero)aryl C-H Bonds with Arylsilanes Using a Removable Auxiliary.
Ni(II)-catalyzed ortho-arylation of aromatic and heteroaromatic carboxamides with triethoxy(aryl)silanes assisted by a removable bidentate auxiliary is reported. This transformation features a broad
A General Strategy for the Nickel-Catalyzed C-H Alkylation of Anilines.
The C-H alkylation of aniline derivatives with both primary and secondary alkyl halides was achieved with a versatile nickel catalyst of a vicinal diamine ligand. Step-economic access to
Nickel-Catalyzed C–H Alkynylation of Anilines: Expedient Access to Functionalized Indoles and Purine Nucleobases
C–H alkynylations of electron-rich anilines were accomplished by means of user-friendly nickel catalysis by enabling transformative nickel-catalyzed C–H functionalization with purine nucleobases through monodentate chelation assistance.
Nickel-catalyzed direct alkynylation of C(sp2)–H bonds of amides: an “inverse Sonogashira strategy” to ortho-alkynylbenzoic acids
The efficiency and selectivity of this strategy provide sustainable routes to a diverse array of ortho-alkynylbenzoic acids under Ni(II)-catalyzed conditions.
Nickel-catalyzed C-H alkylations: direct secondary alkylations and trifluoroethylations of arenes.
A versatile nickel catalyst allowed for C-H alkylations of unactivated arenes with challenging secondary alkyl bromides and chlorides with ample substrate scope.
Efficient direct 2,2,2-trifluoroethylation of indoles via C-H functionalization.
A novel highly C3 selective metal free trifluoroethylation of indoles using 2,2,2-trifuoroethyl(mesityl)-iodonium triflate was developed and quantum chemical calculations provide a deeper understanding of the transformation.
Nickel-catalyzed ortho-halogenation of unactivated (hetero)aryl C-H bonds with lithium halides using a removable auxiliary.
This protocol provides an efficient access to ortho-halogenated (hetero)arenes with operational simplicity, good functional group tolerance, and large-scale synthesis.
Nickel(II)‐Mediated Regioselective CH Monoiodination of Arenes and Heteroarenes by using Molecular Iodine
The 8-aminoquinoline-directed, nickel(II)-mediated ortho-iodination of benzamides using molecular iodine has been developed and provided monoiodinated products in good to excellent yields.