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26.11.2.1.7.1 Variation 1: Ferrier and Petasis Rearrangement

DOI: 10.1055/sos-SD-026-01162

Harrison-Marchand, A.; Chataigner, I.; Maddaluno, J.Science of Synthesis, (2005261247.

The Ferrier rearrangement appears to be a general route to generate the oxo group of chalcogeno ketones. First described by Ferrier in 1979,[‌229‌] the reaction has been largely used to obtain functionalized β-hydroxy cyclohexanones from vinylic carbohydrates and is the subject of a review.[‌230‌] The reaction conditions originally required the use of stoichiometric amounts of mercury(II) chloride, although since then, the more electrophilic mercury(II) acetate,[‌231‌] sulfate,[‌232‌‌234‌] and trifluoroacetate[‌235‌‌237‌] have been shown to be more efficient in adding to the alkene. In these cases, the cyclization of the oxymercurial intermediate generated appears to be more difficult but is easily overcome by addition of chloride anions. The use of the highly reactive mercury(II) sulfate or trifluoroacetate has permitted a catalytic version of the reaction to be developed. The latter is most widely used, requiring less than 10mol% of the salt, but the former proves more selective in cases where two electron-rich double bonds are present in the molecule.[‌234‌] When sensitive protecting groups, such as siloxy, are present in the substrate the use of an acetate buffer is beneficial in preventing hydrolysis.[‌238‌] The Ferrier rearrangement generally leads to cyclohexanones bearing a β-hydroxy group in the axial position and hypotheses are proposed to rationalize this stereoselectivity.[‌230‌]

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