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Enantioselective Halogenative Semi-Pinacol Rearrangement: Extension of Substrate Scope and Mechanistic Investigations

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Published in Chemistry - A European Journal. 2015, vol. 21, no. 14, p. 5561-5583
Abstract 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/semi-pinacol 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.
Keywords HalogenationKinetic isotopic effectLinear free-energy relationshipReaction kineticsSemi-pinacol rearrangement
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Other version: http://doi.wiley.com/10.1002/chem.201406133
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ROMANOV MICHAILIDIS, Fedor et al. Enantioselective Halogenative Semi-Pinacol Rearrangement: Extension of Substrate Scope and Mechanistic Investigations. In: Chemistry - A European Journal, 2015, vol. 21, n° 14, p. 5561-5583. https://archive-ouverte.unige.ch/unige:55654

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Deposited on : 2015-04-21

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