The facile 1,4-migration of Pd between a vinylic position and an arene and between the ortho positions of biaryl compounds have recently been reported. Aryl to benzylic and alkyl to aryl Pd migrations are also known. Herein we report a novel, consecutive vinylic to aryl to allylic Pd ...
6.3.6.3.2Epoxidation of vinyl allenic alcohols Since epoxidation at the vinyldouble bondis unproductive, it is desirable to direct reaction on theallenemoiety. This can be accomplished by taking advantage of the hydroxy-directed epoxidation ofallylic alcoholsusing thet-butyl hydroperoxide/vanadium(V)...
Enantioselectivities vary according to a delicate balance of factors (Table 10), including the identities of the vinyl substituent, nucleophile, catalyst, and leaving group (carbonate vs. phosphate). For example, (S)-BINAPO gives useful ees for 2-aryl cyclohexene derivatives, but distant groups ...
the Skrydstrup group elegantly succeeded the catalytic carbonylation of primary benzylic electrophile using a nickel pincer complex with a CO-gen precursor via the slow addition of Negishi reagent to circumvent the direct Negishi coupling, although the use of allyl electrophiles received limited success ...