Electrolytic cleavage allyl ether

Two new routes to allyl vinyl ethers, suitable substrates for Claisen rearrangement, are summarized in Scheme 41 and equation (22) one involves copper-catalysed solvolytic cleavage by an allylic alcohol of (E)-alkenylpentafluorosili-cates available from hydrosilylation of alkynes," and the other is based on the base-promoted reaction of dimethyl diazomethylphosphonate with aliphatic ketones in the presence of an allylic alcohol." Electrolytic synthesis of allylic ethers direct from alkenes has been discussed earlier in this Report (Scheme 11). ... 

Three selective methods to remove protective groups are receiving much attention assisted, electrolytic, and photolytic removal. Four examples illustrate assisted removal of a protective group. A stable allyl group can be converted to a labile vinyl ether group (eq. 4) a /3-haloethoxy (eq. 5) or a /3-silylethoxy (eq. 6) derivative is cleaved by attack at the /3-substituent and a stable o-nitro-phenyl derivative can be reduced to the o-amino compound, which undergoes cleavage by nucleophilic displacement (eq. 7) ° ... 

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