Rhodium(I)-catalyzed stereoselective [4+2] cycloaddition of oxetanols with alkynes through C(sp3)-C(sp3) bond cleavage

An efficient and convenient synthesis of highly functionalized dihydropyrans has been achieved through rhodium(I)-catalysed tandem C(sp(3))-C(sp(3)) bond cleavage and annulation of oxetanols with alkynes. An enantioselective version was enabled using a Binaphine ligand. Excellent site-selectivity and remarkable enantioretention are obtained for 2-substituted oxetanols.