Enecarbamates are shown to be excellent terminating groups for Prins cyclizations. A noteworthy feature of this methodology is the easy, stereoselective construction of the cyclization precursors by alkylation of metalated (E)-enecarbamates with epoxides. The stereochemistry of the resultant trisubstituted (E)-enecarbamates is then transferred with high fidelity to afford the frequently observe...

The first examples of highly enantioselective Narasaka-Heck cyclizations are described. A SPINOL-derived P,N-ligand system enables Pd-catalyzed 5-exo cyclization of a range of oxime esters with sterically diverse trisubstituted alkenes to generate dihydropyrroles containing tetrasubstituted nitrogen-bearing stereocenters in 56 to 86% yield and 90 : 10 to 95 : 5 e.r. These processes are rare exa...

Using N-sulfonyl triazoles as substrates, compounds as diverse as 2-imino tetrahydrofurans, 13and 15membered ring aza-macrocycles can be prepared selectively via formal [1 + 4], [5 + 4 + 4] and [3 + 4 + 4 + 4] condensations of a-imino carbenes and oxetanes under Rh(II)-catalysis or thermal activation. Spirocyclic N-heterocycles are also accessible by means of Buchwald–Hartwig and Pictet–Spengle...

Abstract: The presence of rather complicated alkaloids in Nitraria species as racemates suggests a non-enzymic biosynthesis of the skeletons, which implies that these reactions should be reproducible in the lab. In the case of Nitramine and Nitraramine the total synthesis was approached starting from highly symmemc glutarimide derivatives. Insight in the biosynthesis of Nitraria alkaloids led t...

The generation of sulfonyl radicals from sulfonyl azides using visible light and a photoactive iridium complex in THF is described. This process was used to promote sulfonylative and azidosulfonylative cyclizations of enynes to give several classes of highly functionalized heterocycles. The use of THF as the solvent is critical for successful reactions. The proposed mechanism of radical initiat...

Gold(I) acetylide and σ,π-digold(I) alkyne complexes derived from one prototypical 1,6-enyne and from 7-ethynyl-1,3,5-cycloheptatriene have been prepared and structurally characterized. Their possible role in gold(I)-catalyzed cycloisomerizations has been studied by experiment and by DFT calculations. Gold(I) acetylides are totally unproductive complexes in the absence of Brønsted acids. Simila...