Cobalt-catalyzed hydroxymethylation of terminal alkynes

Primary propargylic alcohols are important synthetic intermediates in organic chemistry. We have developed a cobalt-catalyzed hydroxymethylation reaction of terminal alkynes and paraformaldehyde under neutral conditions. A variety of primary propargylic alcohols bearing different functional groups have been synthesized. The utilization of tridentate bisoxazoline-phosphine ligand and the hexafluoroisopropyl alcohol solvent are essential for the high reactivity. The mild reaction allows the one-pot synthesis of α,β-unsaturated aldehydes from terminal alkynes and paraformaldehyde via hydroxymethylation/isomerization sequence.