Gold(I)-Catalyzed Reactions of -Glycals with Propargyl Esters toward C-1 Alkenyl Spirocyclopropyl Carbohydrates.

An atom-economic and diazo-free strategy for the construction of novel pseudo anomeric C-1 alkenyl spirocyclopropyl sugars is described. Leveraging the 1,2-migration pathway of propargyl esters under gold(I) catalysis, easily available -glycals undergo β-selective alkenylcarbenoid insertion in moderate to excellent yields. Preferential activation of propargyl moieties and concerted [2 + 1] insertion are both favored through ligand choice and electron enrichment of esters.

-Dichlorobis(XPhos)palladium(II) Precatalyst for Suzuki-Miyaura Cross-Coupling Reactions of Aryl/Vinyl Sulfonates/Halides: Scope, Mechanistic Study, and Synthetic Applications.

Suzuki-Miyaura cross-coupling reactions of aryl/vinyl sulfonates/halides with various boron species were performed using an easily available -dichlorobis(XPhos)palladium(II) precatalyst. Under microwave assistance, more than 30 coupling products were obtained with yields ranging from 23 to 99%, including the synthesis of two bioactive compounds, dubamine and tamoxifen. A mechanistic investigation of the Suzuki-Miyaura reaction was conducted notably by nuclear magnetic resonance (NMR) and high-resolution mass spectroscopy, revealing the nature of the active Pd species and of the reducing entity.