A Rh(I)-catalyzed cycloisomerization of homo- and bis-homopropargylic alcohols

The ability to form rhodium-vinylidene complexes in situ from terminal alkynes has led to the development of a catalytic process, the cycloisomerization of homopropargylic and bis-homopropargylic alcohols to dihydrofurans and dihydropyrans. Among the transition metals that perform similar reactions, rhodium catalysts demonstrate the best chemoselectivity and turnover numbers to date. Both secondary and tertiary alcohols participate equally well. The presence of proparylic oxygen and nitrogen functionality, which potentially can be induced to ionize via formation of allenylidene metal complexes, is compatible with this catalyst. The formation of a 5-amino-dihydropyran which is not compatible with some of the previous catalysts proceeds in good yield with the rhodium catalysts. A substrate bearing a benzylic hydroxyl group adjacent to an electron-rich aromatic ring also participates without complications of ionization. The method provides access to useful aminosugars. A mechanism to account for the different selectivity of this catalyst as compared to others is proposed. Copyright © 2003 American Chemical Society.