Catalytic enantioselective dihalogenation of allylic alcohols [electronic resource]
- Frederick James Seidl.
- Physical description
- 1 online resource.
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|3781 2018 S||In-library use|
- Enantioselective dihalogenation is an important method for the total synthesis of stereocomplex polyhalogenated natural products, but only a few methods with significant limitations currently exist for this transformation. In 2015, we developed the chemo-, regio- and enantioselective bromochlorination of allylic alcohols featuring a titanium half-salen catalyst to help address this problem. The utility of this method has been demonstrated by the enantioselective total syntheses of 11 halogenated natural products to date by our lab, each of which was directly enabled by this method. Following development, we applied the enantioselective bromochlorination to various new substrates including homoallylic alcohols, which resulted in the total synthesis of (--)-anverene, a polyhalogenated marine natural product with modest but selective antibiotic activity. Computational and experimental mechanistic work was undertaken to better understand the catalytic enantioselective bromochlorination, as well as the enantiospecific solvolysis of resulting enantioenriched bromochlorides. The enantioselective dihalogenation catalyst system has also been extended to new reactions using other electrophile-nucleophile pairs, including haloazidation, which uses TMSN3 as the nucleophilic azide source.
- Publication date
- Submitted to the Department of Chemistry.
- Thesis (Ph.D.)--Stanford University, 2018.
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