Stereoselective formation of phenylthio groups substituted 1-metalla-3-titanacyclobutanes

► 1-Metalla-3-titanacyclobutans were synthesized by desulfurizative titanation. ► Structures of the titanacycles were elucidated by X-ray analysis. ► Substituted 1-metalla-3-titanacyclobutans were formed with trans-selectively.