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Enantioselective Halogenative Semi-Pinacol Rearrangement: Extension of Substrate Scope and Mechanistic Investigations |
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Published in | Chemistry. 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 | Halogenation — Kinetic isotopic effect — Linear free-energy relationship — Reaction kinetics — Semi-pinacol rearrangement | |
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Citation (ISO format) | 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. doi: 10.1002/chem.201406133 https://archive-ouverte.unige.ch/unige:55654 |