RESUMO
We introduce an advancement in Morita-Baylis-Hillman (MBH) chemistry that provides access to α-spirannulated enones. The treatment of enone-tethered azaarenium salts with catalytic amounts of organophosphines provides spiroindenyl dihydropyridines. It represents the α-spirannulation of enones via an intramolecular MBH (IMBH) reaction utilizing dual phosphine- and anion-binding catalysis. The IMBH adducts were subjected to several post-synthetic modifications to access highly functionalized molecules.
RESUMO
We describe a diversity-oriented one-pot telescopic synthesis of various benzo[b]carbazoles with the naphthannulation of indoles as the key step, enabled by an intramolecular furan-olefin Diels-Alder reaction. This strategy is general and efficient across a wide range of substrates. We applied this method to synthesize and characterize the first benzo[b]carbazole-based liquid crystalline materials, where the unique molecular design led to the formation of a rare nematic phase at room temperature.
RESUMO
Simultaneous dearomatizing spirannulation of pyridinium salts is still in its infancy. Here, we present an organized skeletal remodeling of designed pyridinium salts by utilizing an interrupted Corey-Chaykovsky reaction to access unprecedented and structurally intriguing molecular architectures such as the vicinal bis-spirocyclic indanones and spirannulated benzocycloheptanones. This hybrid strategy rationally merges the nucleophilic features of sulfur ylides with the electrophilic pyridinium salts to achieve the regio- and stereoselective synthesis of new classes of cyclopropanoids. The plausible mechanistic pathways were derived from experimental results and control experiments.