CuCl2-mediated intramolecular C-H/C-H cross-dehydrogenative coupling (CDC) of thioalkyl-substituted α-acetyl or α-aroyl ketene N,S-acetals afforded 2-thioalkyl indoles. Tunable C-S bond transformations of the resultant indoles led to highly functionalized N-heterocyclic compounds. A β-thioalkyl is necessary to activate the N,S-acetal substrate and enable the CDC reaction to occur, and the relev...

Sequential Wolff rearrangement of α-diazo-β-ketoesters followed by trapping of the ketene intermediates with enol ethers generated a variety of γ,δ-unsaturated β-ketoesters. This method involves a novel thermal cascade reaction and allows the synthesis of γ,δ-unsaturated β-ketoesters with trans-stereochemistry under catalyst-free conditions. The synthesized compounds were further transformed in...

Based on a preactivation protocol with (p-Tol)2SO/Tf2O, a practical, straightforward, and high-yielding synthesis of α-sialyl C-glycosides was accomplished by coupling N-acetyl-5-N,4-O-oxazolidione protected thiosialoside with various trimethylsilyl enol ethers and allyltrimethylsilanes. High yields and excellent α-selectivities were obtained for the strong π-nucleophiles with large nucleophili...

The reaction of 3-benzoylpyrrolo[2,1-c][1,4]benzoxazin-1,2,4-trione with N-(4-bromophenyl)-1-(4-methoxyphenyl)methanimine under thermolytical conditions afforded 4-benzoyl-2-(4-bromophenyl)-1-(4-methoxyphenyl)-1,2-dihydropyrimidino[4,3-c][1,4]benzoxazine-3,5-dione in a good yield. proceeded via situ generation reactive intermediate, acyl(imidoyl)ketene. compound was fully characterized.

Stereo- and chemodivergent enantioselective reaction pathways are observed upon treatment of alkylarylketenes and trichloroacetaldehyde (chloral) with N-heterocyclic carbenes, giving selectively either β-lactones (up to 88:12 dr, up to 94 % ee) or α-chloroesters (up to 94 % ee). Either 2-arylsubstitution or an α-branched iPr alkyl substituent within the ketene favours the chlorination pathway, ...