A Ag (I)-catalyzed synthesis of chiral C (3)-substituted phthalides (8a–f) via a Sakurai– Hosomi allylation/transesterification reaction is described (ee≤ 86%). A notable feature of this reaction is that it utilizes ortho-substituted aldehydes, which are a class of compounds that generally afford poor levels of stereoinduction when applying most known catalytic asymmetric allylation approaches. It was also found that elongation of the n-alkyl chain ...