An anodic cyclization-Friedel Crafts alkylation strategy has been used to rapidly assemble the core ring system of alliacol A and to complete a formal total synthesis of the natural product. The anodic cyclization reaction was used to effect the coupling of a nucleophilic furan ring to the normally nucleophilic carbon of a silyl enol ether. The substrate for this initial cyclization reaction co...

The conceptually construction of axially chiral indolostilbenesi.eN-(2-{(E)-2-[2'-(1-Acetyl-1H-indol-2-yl)-3'chloro4,4',6,6'-tetramethoxy[1,1'-biphenyl]-2yl]ethenyl}phenyl)acetamide and N-(2-{(E)-2-[2'-(1-Acetyl-1H-indol-2-yl)-3'-chloro-2,4',6,6'tetramethoxy[1,1'-biphenyl]-4-yl]ethenyl}phenyl) acetamide are described in this paper. These structure, were obtained by the tactical combination of p...

Light-induced cyclization of several substituted 2-(2-fluorophenylazo)azines in the presence of Ca(2+) ions to the corresponding triazinium derivatives is investigated experimentally and computationally. The azo derivatives of 4-methylpyridine 4 undergo facile cyclization to the corresponding triazinium 1, and the rate of cyclization increases with increasing number of fluorine atoms at the ben...

A detailed kinetic study of the endo-selective epoxide-opening cascade reaction of a diepoxy alcohol in neutral water was undertaken using (1)H NMR spectroscopy. The observation of monoepoxide intermediates resulting from initial endo and exo cyclization indicated that the cascade proceeds via a stepwise mechanism rather than through a concerted one. Independent synthesis and cyclization of the...

Cyclization of linear peptidyl precursors produced by nonribosomal peptide synthetases (NRPSs) is an important step in the biosynthesis of bioactive cyclic peptides. Whereas bacterial NRPSs use thioesterase domains to perform the cyclization, fungal NRPSs have apparently evolved to use a different enzymatic route. In verified fungal NRPSs that produce macrocyclic peptides, each megasynthetase t...

Enantioselective control of the chirality of a tertiary a-carbon in the products of a Nazarov cyclization of enones is challenging because the reaction involves an enantioselective proton transfer process. We herein report the use of cooperative catalysis using Lewis acids and chiral Brønsted acids to control the stereochemistry of the tertiary a-carbon in the products of this reaction. Specifi...

Palladium-catalyzed oxidative cyclization of alkenols provides a convenient entry into cyclic ethers but typically proceeds with little or no diastereoselectivity for cyclization of trisubstituted olefins to form tetrahydrofurans due to the similar energies of competing 5-membered transition-state conformations. Herein, a new variant of this reaction has been developed in which a PdCl2/1,4-benz...

Metal carbenes are often proposed as reactive intermediates in the late transition metal-catalysed transformations of alkynes. Owing to their high reactivity, however, isolation and structural characterization of metal carbene intermediates in these transformations has remained unknown. Herein, we report the isolation of two acyclic gold and copper carbene intermediates in either Au(I)- or Cu(I...

Density functional theory is used to study the mechanism of the title reaction, one of the first catalytic asymmetric 6π-electrocyclizations observed experimentally. The benzylideneacetone-derived phenyl hydrazone is chosen as model substrate for the cyclization reaction, both in the protonated (A) and unprotonated (B) form, while the isoelectronic carbon analogue, 1,5-diphenylpentadienyl anion...

The effects of solvent, temperature, time, weight percent of catalyst on the rate and mechanism of cyclization of natural rubber (NR) was studied in toluene and xylene solutions having tin tetra chloride catalyst (SnCl4). Iodometric titration show, with 8% SnCl4 (based on polymer weight) cyclization occurs, leaving 27.4% of the total unsaturation. Infrared spectra of c...