RESUMEN
The first systematic study of catalytic enantioselective 1,2-additions to acrolein is described. Specifically, using allyl alcohol as a tractable, inexpensive acrolein proelectrophile, iridium-catalyzed acrolein allylation is achieved with high levels of regio-, anti-diastereo-, and enantioselectivity. This process delivers 3-hydroxy-1,5-hexadienes, a useful compound class that is otherwise challenging to access via enantioselective catalysis. Two-fold use of this method unlocks concise total syntheses of amphidinolide R (9 vs 23 steps, LLS) and amphidinolide J (9 vs 23 or 26 steps, LLS), which are prepared in fewer than half the steps previously possible, and the first total synthesis of amphidinolide S (10 steps, LLS).
Asunto(s)
Alcoholes , Compuestos Alílicos , Acroleína , EstereoisomerismoRESUMEN
The first metal-catalyzed oxidative alkynylations of primary alcohols or aldehydes to form α,ß-acetylenic ketones (ynones) are described. Deuterium labelling studies corroborate a novel reaction mechanism in which alkyne hydroruthenation forms a transient vinylruthenium complex that deprotonates the terminal alkyne to form the active alkynylruthenium nucleophile.
RESUMEN
Formate-mediated reductive cross-couplings of vinyl halides with aryl iodides via palladium(I) catalysis occur with highly uncommon cine-substitution. The active dianionic palladium(I) catalyst, [Pd2I4][NBu4]2, is generated in situ from Pd(OAc)2, Bu4NI, and formate. Oxidative addition of aryl iodide followed by dissociation of the dimer provides the monomeric anionic T-shaped arylpalladium(II) species, [Pd(Ar)(I)2(NBu4)], which, upon vinyl halide carbopalladation, forms products of cine-substitution by way of palladium(IV) carbenes, as corroborated by deuterium-labeling experiments.
RESUMEN
A process for 3-fold scaffold diversification is achieved via ruthenium-catalyzed oxidative alkynylation of commercially available oxetanols, azetidinols and bicyclopentanols to form α,ß-acetylenic ketones (ynones), which are subsequently converted to oxetane-, azetidine- and bicyclopentane-bearing pyrazoles, isoxazoles and pyrimidines. A one-pot oxidative alkynylation-condensation protocol that directly converts azetidinols to azetidine-substituted pyrazoles or pyrimidines is demonstrated.
RESUMEN
O-Acetyl 1,3-propanediol serves as an acrolein proelectrophile in π-allyliridium-C,O-benzoate-catalyzed carbonyl allylations mediated by racemic α-substituted allylic acetates. Using the iridium catalyst modified by (R)-SEGPHOS, a variety of 3-hydroxy-1,5-hexadienes are formed with uniformly high levels of regio-, anti-diastereo-, and enantioselectivity.