Straightforward access to [1,2]-annulated indoles, key substructures in natural products, is highly desirable yet challenging. Herein, a radical triggered fragmentary cyclization cascade reaction of ene-ynamides presented, providing rapid into indoles by an intermolecular addition, intramolecular cyclization, desulfonylative aryl migration, and site-selective C(sp2)-N sequence. DFT calculations...

Cyclotides are diverse plant backbone cyclized peptides that have attracted interest as pharmaceutical scaffolds, but fundamentals of their biosynthetic origin remain elusive. Backbone cyclization is a key enzyme-mediated step of cyclotide biosynthesis and confers a measure of stability on the resultant cyclotide. Furthermore, cyclization would be desirable for engineered peptides. Here we repo...

this work described one pot syntheses of polysubstituted 2,6- dicyanoaniline and 2-(3-oxo-1,3-diarylpropyl) malononitrile derivatives in the presence of mgo nanoparticles (nps) under grinding conditions and microwave irradiation, respectively. the simple experimental procedure includes shorter reaction times, higher yields, lower cost and environmental friendliness. other remarkable features ar...

We here describe a new palladium-catalyzed oxidative 6-exo-trig cyclization of 1,6-enynes at room temperature using tBuONO as an oxidant for the synthesis of 3-bicyclo[4.1.0]heptan-5-ones. This cascade strategy involves the hydration, cyclization and cyclopropanation sequence, and represents a new transition-metal-catalyzed oxidative cyclization of 1,6-enynes in a 6-exo-trig fashion.

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 cyclized nr show decreased ...

A mild, visible-light-induced, regioselective cascade sulfonylation-cyclization of 1,5-dienes with sulfonyl chlorides through the intermolecular radical addition/cyclization alkenes C(sp2)-H was developed. This procedure proceeds well and affords a mild efficient route to range monosulfonylated pyrrolin-2-ones at room temperatures.

Peptides can serve as versatile cancer-targeting ligands and have been used for clinically relevant applications such as cancer imaging and therapy. A current and long-standing focus within peptide research is the creation of structurally constrained peptides generated through cyclization. Cyclization is envisioned to enhance the selective binding, uptake, potency and stability of linear precur...

The emergence of terpene cyclization was critical to the evolutionary expansion of chemical diversity yet remains unexplored. Here we report the first discovery of an epistatic network of residues that controls the onset of terpene cyclization in Artemisia annua. We begin with amorpha-4,11-diene synthase (ADS) and (E)-β-farnesene synthase (BFS), a pair of terpene synthases that produce cyclic o...

The synthesis and cyclization of acyclic quinoxaline, pyridine, and pyrimidine enediynes (1-3) are described. These compounds were prepared using palladium(0) coupling of trimethylsilyl acetylene to o-dihaloor o-halotriflic heteroarenes. All compounds were prepared in modest to good yields. The enediynes prepared were shown to undergo Bergman cyclization. Kinetics over a minimum of 3 half-lives...

The cyclizations of two structurally similar 2-oxo-5-hexenyl-type radicals have been investigated by ab initio and density functional (UB3LYP/6-31+G**//UHF/6-31G* and UB3LYP/6-31G*//UB3LYP/6-31G*) calculations. The origin of apparently contradictory reports of 6-endo and 5-exo cyclizations is determined. Kinetic control favors 6-endo cyclization, while thermodynamic control gives 5-exo cyclizat...