Rhodium-Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans.

A comprehensive study of a diastereoselective Rh-catalyzed cyclization of terminal and internal allenols is reported. The methodology allows the atom economic and highly syn-selective access to synthetically important 2,4-disubstituted and 2,4,6-trisubstituted tetrahydropyrans (THP). Furthermore, its utility and versatility are demonstrated by a great functional-group compatibility and the enantioselective total synthesis of (-)-centrolobine.