protonation of the reactive intermediate produced in the  reaction between trimethyl phosphite and dimethyl acetylenedicarboxylate or diethyl acetylenedicarboxylate by resorcinol, 5-methylresorcinol, 2,5-dihydroxyacetophenone, 4-chloro-2-methylphenol, 4-chloro-3,5-dimethy-lphenol, 4-hydroxypyridine, 2-hydroxypyridine, 3-hydroxypyridine, or 8-hydroxyquinoline leads to vinylphosphonium salts, whi...

Transition-metal-catalyzed conjugate addition of organometallics to activated alkenes is an important process.1 Intense research has focused on the utility of copper2 and rhodium catalysts for asymmetric additions,3 and recent efforts have led to the introduction of effective palladium4 catalysts. Each catalyst system exhibits a unique reactivity profile. The rhodium-catalyzed asymmetric conjug...

Protonation of the reactive intermediate produced in the  reaction between trimethyl phosphite and dimethyl acetylenedicarboxylate or diethyl acetylenedicarboxylate by resorcinol, 5-methylresorcinol, 2,5-dihydroxyacetophenone, 4-chloro-2-methylphenol, 4-chloro-3,5-dimethy-lphenol, 4-hydroxypyridine, 2-hydroxypyridine, 3-hydroxypyridine, or 8-hydroxyquinoline leads to vinylphosphonium salts,...

The tandem Friedel-Crafts conjugate addition/asymmetric protonation reaction between 2-substituted indoles and methyl 2-acetamidoacrylate is reported. The reaction is catalyzed by (R)-3,3'-dibromo-BINOL in the presence of stoichiometric SnCl(4), and is the first example of a tandem conjugate addition/asymmetric protonation reaction using a BINOL·SnCl(4) complex as the catalyst. A range of indol...

The first enantioselective organocatalytic amine conjugate addition has been successfully developed. The application of LUMO-lowering iminium catalysis has enabled the highly chemo- and enantioselective 1,4-addition of a rationally designed N-silyloxycarbamate nucleophile (HOMO-raised) to alpha,beta-unsaturated aldehydes. Imidazolidinone 2*pTSA was found to catalyze the addition of various orth...