We report the application of our rhodium-catalyzed nucleophilic ring-opening methodology to the enantioselective synthesis of nitrogen-substituted polycyclic heterocycles. By using a cationic Rh(I) triflate catalyst in the presence of the chiral Josiphos ligand PPF-PtBu2, the ring opening reactions on dihydrooxaquinoline and dihydrooxaisoquinoline using different nucleophiles afford access to multiple dihydroquinolines and dihydroisoquinolones in high yield and high enantioselectivity (up to 99% total yield and >99%ee). A variety of nucleophiles were shown to be compatible with the catalytic system. The electronic effects in the new ring opening reactions were investigated using a variety of nucleophiles. It was found that reactivity and enantioselectivity of the ring opening products depends on the electronic effects as well as the position of the substituents on the substrates. Good yields and high ee of regioisomeric products are obtained using electron donating substituents, whereas electron withdrawing substituents decelerate the reactions.
| Identifer | oai:union.ndltd.org:TORONTO/oai:tspace.library.utoronto.ca:1807/18931 |
| Date | 15 February 2010 |
| Creators | Nguyen, Duc Trung |
| Contributors | Lautens, Mark |
| Source Sets | University of Toronto |
| Language | en_ca |
| Detected Language | English |
| Type | Thesis |
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