Heterohelicenes through 1,3-Dipolar Cycloaddition of Sydnones with Arynes: Synthesis, Origins of Selectivity, and Application to pH-Triggered Chiroptical Switch with CPL Sign Reversal.

Regioselective access to heterohelicenes through the 1,3-dipolar cycloaddition of sydnones with arynes is described. Novel access to sydnones and poly(hetero)aromatic aryne precursors allowed the introduction of chemical diversity over multiple positions of the helical scaffolds. The origins of the unconventional regioselectivity during the cycloaddition steps was systematically investigated using density functional theory (DFT) calculations, unveiling the key features that control this reactivity, namely, face-to-face (π···π) or edge-to-face (C-H···π) interactions, primary orbital interactions and distortion from coplanarity in the transition structures (TSs) of the transformation.

Recent advances in the stereoselective synthesis of acyclic all-carbon tetrasubstituted alkenes.

Alkenes bearing four carbon-based groups are ubiquitous motifs in chemical sciences due to their various applications from medicinal to materials chemistry, and as chemical platforms for the synthesis of complex, chiral molecules. As such, tremendous research efforts are currently ongoing in order to develop general procedures for the challenging stereoselective synthesis of all-carbon tetrasubstituted alkenes, especially for acyclic structures. Since classical approaches to carbon-carbon double bonds are not suitable for the high steric demand around tetrasubstituted alkenes, a variety of unique approaches to access these privileged functional groups have been developed in recent years.

Organocatalytic aza-Michael Reaction to 3-Vinyl-1,2,4-triazines as a Valuable Bifunctional Platform.

An unprecedented catalytic aza-Michael addition to substituted 3-vinyl-1,2,4-triazines, as original bifunctional platforms for the domino conjugate addition inverse-electron-demand hetero-Diels-Alder/retro-Diels-Alder ( ihDA/ rDA) reaction, was achieved using the highly acidic triflimide as an organocatalyst. Based on the use of alkoxyamine nucleophiles, this sequence not only highlights a rare example of the catalytic aza-Michael reaction to alkenylazaarenes but also proves to be useful for the elaboration of an array of biorelevant tetrahydro-[1,6]-naphthyridines.

Domino Aza-Michael-ih-Diels-Alder Reaction to Various 3-Vinyl-1,2,4-triazines: Access to Polysubstituted Tetrahydro-1,6-naphthyridines.

A straightforward domino aza-Michael-inverse-electron-demand-hetero-Diels-Alder/retro-Diels-Alder reaction between primary and secondary propargylamine derivatives and 3-vinyl-1,2,4-triazines is developed highlighting not only the uniqueness of this dual-heterocyclic platform but also a novel and unprecedented path to polysubstituted tetrahydro-1,6-naphthyridine scaffolds.