Rapid Access to β-Trifluoromethyl-Substituted Ketones: Harnessing Inductive Effects in Wacker-Type Oxidations of Internal Alkenes
Online Publication Date2014-07-18
Print Publication Date2014-08-11
Permanent link to this recordhttp://hdl.handle.net/10754/599440
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AbstractWe present a practical trifluoromethyl-directed Wacker-type oxidation of internal alkenes that enables rapid access to β-trifluoromethyl-substituted ketones. Allylic trifluoromethyl-substituted alkenes bearing a wide range of functional groups can be oxidized in high yield and regioselectivity. The distance dependence of the regioselectivity was established by systematic variation of the number of methylene units between the double bond and the trifluoromethyl group. The regioselectivity enforced by traditional directing groups could even be reversed by introduction of a competing trifluoromethyl group. Besides being a new powerful synthetic method to prepare fluorinated molecules, this work directly probes the role of inductive effects on nucleopalladation events. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
CitationLerch MM, Morandi B, Wickens ZK, Grubbs RH (2014) Rapid Access to β-Trifluoromethyl-Substituted Ketones: Harnessing Inductive Effects in Wacker-Type Oxidations of Internal Alkenes. Angew Chem Int Ed 53: 8654–8658. Available: http://dx.doi.org/10.1002/anie.201404712.
SponsorsWe gratefully acknowledge financial support from the King Abdullah University of Science and Technology Centre in Development, King Fahd University of Petroleum and Minerals, and the NSF. Furthermore, we thank the Gordon and Betty Moore Foundation, the SNSF for a fellowship to B.M., and the Swiss Study Foundation for a fellowship to M.M.L.
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