Lewis acid-catalyzed reaction of allyl and benzyl trichloroacetimidates with r-silyl alcohols was found to be a general method for the synthesis of r-alkoxysilanes. Upon exposure to CsF, these r-alkoxysilanes could be made to undergo [2,3]-Wittig rearrangement with an efficiency similar to that realized by the analogous but inherently more toxic r-alkoxystannanes. For over 20 years Wittig rearr...

The combination of small-molecule catalysis and enzyme represents an underexploited area research with huge potential in asymmetric synthetic chemistry due to both compatibility reaction conditions complementary reactivity. Herein, we describe the telescopic synthesis chiral nitro alcohols starting from commercially available benzaldehyde derivatives through one-pot three-step chemoenzymatic ca...

stable crystalline phosphorus ylides are obtained in excellent yields from the 1:1:1 addition reactionbetween hydantoins or thiohydantoins and dialkyl acetylenedicarboxylates in the presence oftriphenylphosphine. these phosphoranes undergo smooth intramolecular wittig reaction followedby an electrocyclic ring opening to produce dialkyl (e)-2-(2,5-dihydro-5,5-diaryl-2-thioxo-1h-imidazol-4-yl)fum...

Aza-Heck cyclizations initiated by oxidative addition of Pd(0) -catalysts into the N-O bond of N-(pentafluoro-benzoyloxy)sulfonamides are described. These studies, which encompass only the second class of aza-Heck reaction developed to date, provide direct access to diverse N-heterocyclic ring systems.

Key words (±)-talatisamine - Diels–Alder reaction [2+2] photo-cycloaddition Lemieux–Johnson oxidation retro-aldol–aldol Wagner–Meerwein rearrangement aza-Prins

The choice is yours: a highly stereoselective synthesis of α-alkyl-α-hydroxy-β-amino esters is accomplished through a tandem Wittig-rearrangement/Mannich reaction sequence. Transformations of N-benzyl or N-Boc imines proceed with high selectivity for formation of syn-amino alcohol derivatives, whereas N-Boc-2-(phenylsulfonyl)amines generate anti-amino alcohol products. Auxiliary cleavage (trans...