Abstract This paper presents the first acid-free, organocatalytic tetrahydropyran and 2- methoxypropene protection of alcohols, phenols, and other ROH derivatives utilizing privileged N, N′-bis [3, 5-bis (trifluoromethyl) phenyl] thiourea and a polystyrene-bound analogue. The reactions are broadly applicably (also on preparative scale), in particular, to acid-sensitive substrates such as aldol products, hydroxy esters, acetals, silyl-protected ...