Cope rearrangement siloxy

Example 5, Tandem aldol reaction/siloxy-Cope rearrangement  

Mullins, R. J. McCracken, K. W. Cope and Related Rearrangements. In Name Reactions forHomologations-PartII, Li, J. J., Ed. Wiley Hoboken, NJ, 2009, pp 88-135. (Review). 

Schneider, C. Synlett 2001,1079-1091. (Review on siloxy-Cope rearrangement). 

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Silyl ethers of vinyl allyl alcohols can also be used in oxy-Cope rearrangements.215 Known as the siloxy-Cope rearrangement, this methodology has been used in... 

Claisen condensation equivalent, 10, 174 Claisen rearrangement equivalent, 10, 176 enolate alkylation equivalent, 10, 171 Mannich reaction equivalent, 10, 174 as strategic reaction, 10, 171 intermolecular carbene insertion, C-H activation-Cope rearrangement characteristics, 10, 177 as strategic reaction, 10, 178 tandem aldol reaction-siloxy-Cope rearrangement equivalent, 10, 181... 

A method of repetitive ring expansion of cyclic ketones was published based on the use of (phenylseleno)acetaldehyde on the siloxy-Cope rearrangement [29a], The authors were able to transform cyclododecanone into cycloeicosadec-5-en-l-one in 23 % yield. 

Rearrangements. Allyl esters are directly converted to isocyanates when the modified Curtins rearrangement is carried out in the presence of (Ph,P)4Pd. A versatile construction of the core structure of antibiotic CP-263114 is highlighted in a reaction sequence consisting of carbonylation, lactonization, and siloxy-Cope rearrangement. "... 

The syntheses of the related molecules CP-225917 and CP-263114 and other members of the phomoidride family have employed the siloxy-Cope rearrangement as key transformations. In one of the more impressive demonstrations of this concept, Leighton and coworkers utilized the late-stage, tandem carbonylation/siloxy-Cope rearrangement of 96 to provide 98 in outstanding yield. 

In one of the early applications of the siloxy-Cope rearrangement in synthesis, Danishefsky and coworkers utilized the process for the synthesis of 7V-acetylactinobolamine. Rearrangement of 101 resulted in the formation of 102 in good yield. 

Oxy-Cope rearrangements of fluorinated divinylcyclohexanols have afforded access to cyclodecenones containing various numbers of fluorine atoms. The first remarkable examples of reversibility under anionic oxy-Cope conditions have been observed, (121) (122). Siloxy-Cope rearrangements have been used to make bridgehead alkenes related to the core structure of CP-225,917 and CP-263,114. " ... 

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