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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.

chemical science

Rhodium(<scp>i</scp>)-catalyzed stereoselective [4+2] cycloaddition of oxetanols with alkynes through C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond cleavage

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

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