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...

Explaining the oxidation–cyclization mechanism of heterocycles containing Te−O bonds. The structures halogenated Te-containing have been elucidated, and computational methods showed them to be prepared in a two-step oxidation–cyclization. three compounds shown represent both structural diversity biological application these hypervalent as leishmanicides. More information can found Full Paper by...

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...

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...

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...

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...

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...

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...

ABSTRACT Acetonolysis of the titanium tetrachioride complex of lycopene gives s-carotene and e.carotene. Analogous cyclization reactions have been achieved with y-carotene, rubixanthin esters and f3-zeacarotene. In some typical parasitic plants and semi-parasitic plants, carotenoids with a-structures predominate over those with fl-structures. The formation of carotenoid epoxides is favoured in ...

E- and Z-9-Methyldeca-3,8-dien-1-ols undergo smooth cyclization with aldehydes in the presence of 20 mol% AgSbF6 under extremely mild conditions to generate the corresponding oxa-bicycles in good yields with excellent selectivity. In fact, E-olefin affords the trans-product exclusively, whereas the Z-olefin gives the cis-product predominantly. In the case of E- or Z-8-methylnona-3,8-dien-1-ol, ...