Enantioselective halogenative semi-pinacol rearrangement: extension of substrate scope and mechanistic investigations.

Autor: Romanov-Michailidis F; Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4 (Switzerland)., Romanova-Michaelides M, Pupier M, Alexakis A
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2015 Mar 27; Vol. 21 (14), pp. 5561-83. Date of Electronic Publication: 2015 Feb 25.
DOI: 10.1002/chem.201406133
Abstrakt: 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.
(© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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