TY - JOUR A1 - Dreier, Anna-Lena A1 - Matsnev, Andrej V. A1 - Thrasher, Joseph S. A1 - Haufe, Günter T1 - Syn-selective silicon Mukaiyama-type aldol reactions of (pentafluoro-λ6-sulfanyl)acetic acid esters with aldehydes JF - Beilstein Journal of Organic Chemistry PY - 2018/// VL - 14 SP - 373 EP - 380 SN - 1860-5397 DO - 10.3762/bjoc.14.25 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.14.25 KW - aldol reaction KW - ester enolate KW - fluorine KW - SF5 compounds KW - stereochemistry N2 - 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. ER -