Iodoolefinic polypropionate building blocks from vinyl silanes with control of geometry by solvent and by neighboring group participation

Iododesilylation of trisubstituted (Z)-silyl olefins proceeds with retention of geometry in hexafluoroisopropanol (HFIP) but, for unhindered cases, with inversion of geometry in DMSO. When an acyloxy substituent is positioned to participate in the reaction, the protocol consistently leads to inversion of geometry.