| Popis: |
The addition of nucleophiles to SDEs (SDEs), the double oxidation product of allenes, offers a concise and stereoselective method for the preparation of highly functionalized α-hydroxy ketones and ketone derivatives. Disclosed herein are studies of heteronucleophilic and enolate addition to SDEs. In a separate study, silyl SDEs were explored as surrogates for 1,3-disubstituted allenes, resulting in highly regio- and stereoselective oxidation. General methods for the regioselective opening of silyl SDEs by carboxylic acids and hydrides were developed. Titanium reagents were also discovered to open silyl SDEs to provide α-hydroxy enones. Finally, the application of SDE chemistry to planned psymberin analogues and the scale-up of key intermediates is discussed. |
