Enantioselectivity increases with increasing carbonyl electrophilicity in 2-propanol-mediated reductive couplings of aldehydes with branched aryl-substituted allylic acetates to form products of carbonyl anti-(α-aryl)allylation. This unusual phenomenon is caused by aldehyde coordination to diastereomeric kinetic vs thermodynamic carbonyl binding sites that deliver enantiomeric products. Exploiting this effect, anti-diastereo- and enantioselective (α-aryl)allylations of fluoral hydrate and difluoroacetaldehyde ethyl hemiacetal were developed.

An inside job: Enantioselective phthalide synthesis was achieved through internal redox allylation of o-phthalaldehydes. Oxidative esterification is balanced by reductive carbonyl addition to achieve an overall redox-neutral process. This method enabled formal syntheses of ent-spirolaxine methyl ether and CJ-12,954.

The 20-membered marine macrodiolide clavosolide Aisprepared in 7steps (LLS) in the absence of protecting groups or chiral auxiliaries via enantioselective alcoholmediated carbonyl addition. In 9p rior total syntheses,1 1-34 steps (LLS) were required.

Several Gold’s reagents were synthesized from cyanuric chloride and N,N-dialkylformamides. These synthetic equivalents of N,N-dimethylformamide dimethyl acetal were used in an optimized and scalable procedure for the regioselective synthesis of a variety of enaminones from ketone starting materials, whose utility was demonstrated by the stereoselective synthesis of Rawal-type dienes.

Red und Ox: Durch interne Redoxallylierung von o‐Phthalaldehyden wurden Phthalide enantioselektiv synthetisiert. Der insgesamt redoxneutrale Prozess umfasst eine oxidative Veresterung und eine reduktive Carbonyladdition, die sich gegenseitig ausgleichen. Die Methode ermöglichte formale Synthesen von ent‐Spirolaxin‐Methylether und CJ‐12,954.