Chiral metal catalysts have been widely applied to asymmetric transformations. However, the electronic structure of the catalyst and how it contributes to the activation of the substrate is seldom investigated. Here, we report an empirical approach for providing insights into the catalytic activation process in the distorted Ni(II)-catalysed asymmetric [3+2] cycloaddition of α-ketoesters. We qu...

A divergent asymmetric total synthesis of voacafricines and B, hexacyclic monoterpene indole alkaloids, has been accomplished featuring the following key steps: a) a catalyst-controlled Pictet–Spengler reaction 6-methoxytryptamine with chiral α-ketoester affording 1,1-disubstituted tetrahydro-β-carboline in excellent yield diastereoselectivity; b) oxidative cleavage 3,5-disubstituted cyclopente...

In the last few years we demonstrated the utility of the phthalimidesulfenyl chloride (PhthNSCl, Phth = Phthaloyl) mediated generation of α,α’-dioxothiones and several related thiocarbonyl species. These reactive thione derivatives can be used as efficient electron-poor dienes in inverse electron demand Diels-Alder reactions with a plethora of electron rich alkenes, giving rise to interesting s...

Focusing on the steric and electronic properties of the resonance-stabilized amidine framework, a cationic metal-bisamidine complex was designed as a conjugated combined Lewis-Brønsted acid catalyst. The chiral Zn(II)-bisamidine catalyst prepared from the 2,2'-bipyridyl derived bisamidine ligand, ZnCl₂, and AgSbF₆ promoted asymmetric Mukaiyama aldol reaction of α-ketoester and α,α-disubstituted...

in this work, so3h-functionalizedphthalimide (sfp) as a so3h-containing solid acid is prepared by the reaction of phthalimide with chlorosulfonic acid, and characterized by ft-ir, 1h and 13c nmr, mass, tg, dtg, xrd and sem. then, it is utilized as a highly efficient, heterogeneous and green catalyst for the one-pot multi-component condensation of dimedone with arylaldehydes, β-ketoesters and am...

a highly efficient, simple and clean solvent-free protocol for the synthesis of polyhydroquinolines is described. the one-pot multi-component condensation reaction between arylaldehydes, dimedone (5,5-dimethylcyclohexane-1,3-dione), β-ketoesters and ammonium acetate in the presence of catalytic amount of (2.5 mol%) melamine trisulfonic acid (mtsa) as a recyclable, green and attractive sulfonic ...

A concise approach to the algal metabolite 1 is described, which also determines the previously unknown stereostructure of this natural product. Compound 1 is distinguished by a rare brominated 4-pyrone nucleus linked as a ketene-acetal to a polyunsaturated macrocyclic scaffold comprising an extra homoallylic bromide entity. The synthesis of 1 is based on the elaboration and selective functiona...

The catalytic enantioselective synthesis of densely functionalised organic molecules containing all-carbon quaternary stereocentres is a challenge to modern chemical methodology research. The catalytically controlled asymmetric alpha-alkylation of ketones represents another difficult task and has been of major interest to our and other research groups in the past. We now report a palladium-cata...