Pd-Catalyzed Carbonylative Carboperfluoroalkylation of Alkynes. Through-Space ¹³C–¹⁹F Coupling as a Probe for Configuration Assignment of Fluoroalkyl-Substituted Olefins

A four-component Pd-catalyzed protocol for direct synthesis of perfluoroalkyl-substituted enones is reported. Under mild conditions and low catalyst loading, alkynes, iodoperfluoroalkanes, (hetero)­arylboronic acids, and carbon monoxide are assembled into highly elaborate products with good yields and excellent regio- and stereoselectivities. The configuration of the products was confirmed by the observation of through-space ¹³C–¹⁹F couplings, accessible through the analysis of routine ¹³C NMR spectra

Synthesis of Polyhydroxylated Quinolizidine and Indolizidine Scaffolds from Sugar-Derived Lactams via a One-Pot Reduction/Mannich/Michael Sequence

A direct approach to the synthesis of indolizidine and quinolizidine scaffolds of iminosugars is described. The presented strategy is based on a one-pot sugar lactam reduction with Schwartz’s reagent followed by a diastereoselective Mannich/Michael tandem reaction of the resulting sugar imine with Danishefsky’s diene. The stereochemical course of the investigated reaction has been explained in detail. The obtained bicyclic products are attractive building blocks for the synthesis of various naturally occurring polyhydroxylated alkaloids and their derivatives