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Synthesis of 1,2,4-Trisubstituted-(1H)-imidazoles through Cu(OTf)2-/I2-Catalyzed C-C Bond Cleavage of Chalcones and Benzylamines.

ABSTRACT: 1,2,4-Trisubstituted-(1H)-imidazoles have been synthesized by the Cu(OTf)2- and I2-catalyzed unusual C-C bond cleavage of chalcones and benzylamines. After the ?,?-unsaturated C-C bond cleavage, the ?-portion is eliminated from the reaction. Various aryl- and heteroaryl-substituted chalcones and benzylamines were well tolerated in this unusual transformation to yield the trisubstituted-(1H)-imidazoles.

SUBMITTER: Salfeena CTF

PROVIDER: S-EPMC6644843 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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Synthesis of 1,2,4-Trisubstituted-(1H)-imidazoles through Cu(OTf)2-/I2-Catalyzed C-C Bond Cleavage of Chalcones and Benzylamines.

Salfeena Chettiyan Thodi F CTF Jalaja Renjitha R Davis Rincy R Suresh Eringathodi E Somappa Sasidhar B SB

ACS omega 20180719 7

1,2,4-Trisubstituted-(1H)-imidazoles have been synthesized by the Cu(OTf)2- and I2-catalyzed unusual C-C bond cleavage of chalcones and benzylamines. After the α,β-unsaturated C-C bond cleavage, the β-portion is eliminated from the reaction. Various aryl- and heteroaryl-substituted chalcones and benzylamines were well tolerated in this unusual transformation to yield the trisubstituted-(1H)-imidazoles. ...[more]

PMID: 31458944

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Project description:Current interest in copper/dioxygen reactivity includes the influence of thioether sulfur ligation, as it concerns the formation, structures, and properties of derived copper-dioxygen complexes. Here, we report on the chemistry of {L-Cu(I)}2-(O2) species L = (DMM)ESE, (DMM)ESP, and (DMM)ESDP, which are N3S(thioether)-based ligands varied in the nature of a substituent on the S atom, along with a related N3O(ether) (EOE) ligand. Cu(I) and Cu(II) complexes have been synthesized and crystallographically characterized. Copper(I) complexes are dimeric in the solid state, [{L-Cu(I)}2](B(C6F5)4)2, however are shown by diffusion-ordered NMR spectroscopy to be mononuclear in solution. Copper(II) complexes with a general formulation [L-Cu(II)(X)](n+) {X = ClO4(-), n = 1, or X = H2O, n = 2} exhibit distorted square pyramidal coordination geometries and progressively weaker axial thioether ligation across the series. Oxygenation (-130 °C) of {((DMM)ESE)Cu(I)}(+) results in the formation of a trans-?-1,2-peroxodicopper(II) species [{((DMM)ESE)Cu(II)}2(?-1,2-O2(2-))](2+) (1(P)). Weakening the Cu-S bond via a change to the thioether donor found in (DMM)ESP leads to the initial formation of [{((DMM)ESP)Cu(II)}2(?-1,2-O2(2-))](2+) (2(P)) that subsequently isomerizes to a bis-?-oxodicopper(III) complex, [{((DMM)ESP)Cu(III)}2(?-O(2-))2](2+) (2(O)), with 2(P) and 2(O) in equilibrium (K(eq) = [2(O)]/[2(P)] = 2.6 at -130 °C). Formulations for these Cu/O2 adducts were confirmed by resonance Raman (rR) spectroscopy. This solution mixture is sensitive to the addition of methylsulfonate, which shifts the equilibrium toward the bis-?-oxo isomer. Further weakening of the Cu-S bond in (DMM)ESDP or substitution with an ether donor in (DMM)EOE leads to only a bis-?-oxo species (3(O) and 4(O), respectively). Reactivity studies indicate that the bis-?-oxodicopper(III) species (2(O), 3(O)) and not the trans-peroxo isomers (1(P) and 2(P)) are responsible for the observed ligand sulfoxidation. Our findings concerning the existence of the 2(P)/2(O) equilibrium contrast with previously established ligand-Cu(I)/O2 reactivity and possible implications are discussed.

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).

Dataset Information

Synthesis of 1,2,4-Trisubstituted-(1H)-imidazoles through Cu(OTf)2-/I2-Catalyzed C-C Bond Cleavage of Chalcones and Benzylamines.

Publications

Synthesis of 1,2,4-Trisubstituted-(1<i>H</i>)-imidazoles through Cu(OTf)<sub>2</sub>-/I<sub>2</sub>-Catalyzed C-C Bond Cleavage of Chalcones and Benzylamines.

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