Concise Synthesis of Acetal‐Protected syn 1,3‐Diols by a Tandem Hemiacetal Formation/Tsuji–Trost Reaction

Synthesis of 1,3-Diols by O-Nucleophile Additions to Activated Alkenes

“…Menche and Wang 52 reported the first approach using one of these strategies in 2012. They used a palladium catalyst and acetaldehyde to generate the hemiacetal, and used carbonates as leaving groups (Scheme 23).…”

In situ tether formation from amines and alcohols enabling highly selective Tsuji–Trost allylation and olefin functionalization

“…In 2012, Wang and Menche reported the use of acetaldehyde as tether for the synthesis of syn 1,3-diols via tandem hemiacetal formation and Tsuji–Trost reaction with a simple palladium catalyst ( Scheme 2 ). 13 This 3-step relay process involved (i) hemiacetal formation from a chiral homoallylic alcohols and acetaldehyde, (ii) palladium π-allyl complex formation, and (iii) intramolecular allylic substitution.…”

Sequential catalysis for stereoselective synthesis of complex polyketides

“…10m-p,17 The realization of this concept is depicted in Scheme 6. 18 The most effective conditions for the selective synthesis of syn-1,3dioxanes of type 16 relied on homoallylic alcohol 10 in acetaldehyde as a co-solvent, with a slight excess of KHMDS (1.5 eq.) and catalytic amounts of [Pd(allyl)Cl] 2 (10%) and PPh 3 (30%) at room temperature, in toluene.…”

“…Importantly, the generated terminal alkene functionality may serve as a synthetic handle for the further elaboration of the target, as demonstrated in a fragment synthesis of macrolide RK-397 (not shown). 18…”