Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 21, Issue 14, Pages 5561-5583Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201406133
Keywords
halogenation; kinetic isotopic effect; linear free-energy relationship; reaction kinetics; semi-pinacol rearrangement
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Funding
- Swiss National Research Foundation [200020-126663]
- COST action (SER Contract) [CM0905, C11.0108]
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The present Full Paper article discloses a survey of our recent results obtained in the context of the enantioselective halogenation-initiated semi-pinacol rearrangement. Commencing with the fluorination/semi-pinacol reaction first and moving to the heavier halogens (bromine and iodine) second, the scope and limitations of the halogenative phase-transfer methodology will be discussed and compared. An extension of the fluorination/semi-pinacol reaction to the ring-expansion of five-membered allylic cyclopentanols will be also described, as well as some preliminary results on substrates prone to desymmetrization will be given. Finally, the present manuscript will culminate with a detailed mechanistic investigation of the canonical fluorination/semipinacol reaction. Our mechanistic discussion will be based on in situ reaction progress monitoring, complemented with substituent effect, kinetic isotopic effect and non-linear behaviour studies.
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