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Controllable double CF₂-insertion into sp² C-Cu bond using TMSCF₃: a facile access to tetrafluoroethylene-bridged structures.

ABSTRACT: A highly efficient method for controllable double CF₂-insertion into pentafluorophenylcopper species using TMSCF₃ as difluoromethylene source has been developed. The newly generated fluoroalkylcopper(i) species, C₆F₅CF₂CF₂Cu, shows good reactivity towards a myriad of structurally diverse aryl, heteroaryl and alkenyl iodides. This protocol is easy to handle, ready to scale up and applicable for the synthesis of relative complex molecules, thus providing a convenient method for facile access to tetrafluoroethylene-bridged structures.

SUBMITTER: Xie Q

PROVIDER: S-EPMC8133001 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Copper-dependent metalloenzymes are widespread throughout metabolic pathways, coupling the reduction of O2 with the oxidation of organic substrates. Small-molecule synthetic analogs are useful platforms to generate L/Cu/O2 species that reproduce the structural, spectroscopic, and reactive properties of some copper-/O2-dependent enzymes. Landmark studies have shown that the conversion between dicopper(II)-peroxo species (L2CuII2(O22-) either side-on peroxo, SP, or end-on trans-peroxo, TP) and dicopper(III)-bis(μ-oxo) (L2CuIII2(O2-)2: O) can be controlled through ligand design, reaction conditions (temperature, solvent, and counteranion), or substrate coordination. We recently published ( J. Am. Chem. Soc. 2012 , 134 , 8513 , DOI: 10.1021/ja300674m ) the crystal structure of an unusual SP species [(MeAN)2CuII2(O22-)]2+ (SPMeAN, MeAN: N-methyl-N,N-bis[3-(dimethylamino)propyl]amine) that featured an elongated O-O bond but did not lead to O-O cleavage or reactivity toward external substrates. Herein, we report that SPMeAN can be activated to generate OMeAN and perform the oxidation of external substrates by two complementary strategies: (i) coordination of substituted sodium phenolates to form the substrate-bound OMeAN-RPhO- species that leads to ortho-hydroxylation in a tyrosinase-like fashion and (ii) addition of stoichiometric amounts (1 or 2 equiv) of Lewis acids (LA's) to form an unprecedented series of O-type species (OMeAN-LA) able to oxidize C-H and O-H bonds. Spectroscopic, computational, and mechanistic studies emphasize the unique plasticity of the SPMeAN core, which combines the assembly of exogenous reagents in the primary (phenolates) and secondary (Lewis acids association to the MeAN ligand) coordination spheres with O-O cleavage. These findings are reminiscent of the strategy followed by several metalloproteins and highlight the possible implication of O-type species in copper-/dioxygen-dependent enzymes such as tyrosinase (Ty) and particulate methane monooxygenase (pMMO).

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Controllable double CF₂-insertion into sp² C-Cu bond using TMSCF₃: a facile access to tetrafluoroethylene-bridged structures.

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Controllable double CF2-insertion into sp2 C-Cu bond using TMSCF3: a facile access to tetrafluoroethylene-bridged structures.

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OmicsDI is part of the ELIXIR infrastructure

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Controllable double CF₂-insertion into sp² C-Cu bond using TMSCF₃: a facile access to tetrafluoroethylene-bridged structures.