Simple Lewis pairs of zinc salts and organobases as bifunctional catalysts for controlled ring-opening polymerization of O-carboxyanhydrides

Simple Lewis pairs consisting of organobases and zinc salts were explored to promote ring-opening polymerization of phenyl O-carboxyanhydride via bifunctional catalysis, producing well-defined poly(α-hydroxyalkanoic acid)s with good isotacticity (Pm = 0.88).

Syn-selective silicon Mukaiyama-type aldol reactions of (pentafluoro-λ6-sulfanyl)acetic acid esters with aldehydes

Aldol reactions belong to the most frequently used C–C bond forming transformations utilized particularly for the construction of complex structures. The selectivity of these reactions depends on the geometry of the intermediate enolates. Here, we have reacted octyl pentafluoro-λ6-sulfanylacetate with substituted benzaldehydes and acetaldehyde under the conditions of the silicon-mediated Mukaiyama aldol reaction. The transformations proceeded with high diastereoselectivity. In case of benzaldehydes with electron-withdrawing substituents in the para-position, syn-α-SF5-β-hydroxyalkanoic acid esters were produced. The reaction was also successful with meta-substituted benzaldehydes and o-fluorobenzaldehyde. In contrast, p-methyl-, p-methoxy-, and p-ethoxybenzaldehydes led selectively to aldol condensation products with (E)-configured double bonds in 30–40% yields. In preliminary experiments with an SF5-substituted acetic acid morpholide and p-nitrobenzaldehyde, a low amount of an aldol product was formed under similar conditions.