Ionic Liquid‐Catalyzed C−C Bond Formation for the Synthesis of Polysubstituted Olefins

Abstract

Polysubstituted olefins as attractive and useful compounds are generally acquired by traditional acid or metal catalyzed system. Herein, a convenient and environmentally friendly method using acidic ionic liquid as a metal-free catalyst and dimethyl carbonate (DMC) as a green solvent has been demonstrated to synthesize polysubstituted olefins through construction of new CÀ C bonds by activating of ethers and alkenes. In the system, the usage of metal, halogen, traditional toxic solvents, and a large number of additives was avoided, neutralization after the reaction was not required, and waste production was reduced. The system was suitable for benzyl ethers and styrene derivatives, and recyclable [MeBs(dio)TMP][OTf] exhibited best activity. Density functional theory (DFT) calculations suggest synergistic functions of the cation and anion of ILs and show hydrogen bonds and π-π stacking interactions between catalyst and substrates, which can lead to lower barriers.

Theoretical Investigation of Ag(I) Acid-catalysed Cascade Benz Annulation of N-(3-(2-(4-Methoxybenzoyl)phenyl)prop-2-yn-1-yl)benzamide for Synthesis of Naphthooxazole

“…The geometry optimizations were performed at the B3LYP/ BSI level with the Gaussian 09 package [26,27]. The mixed basis set of LanL2DZ for Ag and 6-31G(d) for nonmetal atoms [28][29][30][31][32] was denoted as BSI. Different singlet and multiplet states were clarified with B3LYP and ROB3LYP approaches including Becke's three-parameter hybrid functional combined with Lee−Yang−Parr correction for correlation [33,34].…”

“…In view of the solvent effect on reaction with ions estimated by our approach [28][29][30][31][32], it's expected to have great impact on this charged system catalyzed by Ag(I) acid. The difference value of absolute energies between in gas phase and DCE solution are listed for all stationary points (Table S1).…”

“…The following nucleophilic addition of H2O is facilitated under the catalysis of Ag, which is completely linked to alkyne C2 (0.21 nm). FMO calculations were applied for typical TSs to get more qualitative evidence of structural analysis [28][29][30][31][32]. The visual orbitals of Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) were analyzed (Figure 3) together with MBO results for the orbital contribution of bonding atoms (Table 2 and Table 3).…”

Theoretical investigation on diastereoselective [2+2] cycloaddition and Pd-catalyzed enantioselective [3+2] cycloaddition for synthesis of cis-β-lactam and exo-furobenzopyranone

“…The geometry optimizations were performed at the B3LYP/BSI level with the Gaussian 09 package [26,27]. The mixed basis set of LanL2DZ for Pd and 6-31G(d) for non-metal atoms [28][29][30][31][32] was denoted as BSI. Different singlet and multiplet states were clarified with B3LYP and ROB3LYP approaches including Becke's three-parameter hybrid functional combined with Lee−Yang−Parr correction for correlation [33][34][35][36][37][38][39].…”