97664-06-7Relevant academic research and scientific papers
INTRAMOLECULAR REARRANGEMENTS: EPIMERIZATION OF BICYCLIC VINYL TERTARY ALCOHOLS VIA A SULFOXIDE SIGMATROPIC REARRANGEMENT
Brown, William L.,Fallis, Alex G.
, p. 1828 - 1833 (2007/10/02)
A general method for inverting the stereochemistry of bicyclic vinyl endo alcohols such as 6 and 12 to give the corresponding exo isomers 10 and 18 is described.The procedures employ a sulfoxide rearrangemnet as a key step.In the case of the norbornene alcohol 12 the intermediate sulfenate ester 13 gives the oxetane 14 rather than the expected sulfoxide 17.It was therefore prepared by thionyl chloride induced rearrangement of 12 to the allylic chloride 15 followed by displacement (PhSNa) and oxidation (m-chloroperbenzoic acid).The exo alcohol thus obtained underwent smooth anionic oxy-Cope rearrangement (KH, THF) to the cis-hydrindenone 19.
EPIMERIZATION OF BICYCLIC VINYL TERTIARY-ALCOHOLS VIA SIGMATROPIC REARRANGEMENT
Brown, William L.,Fallis, Alex G.
, p. 607 - 610 (2007/10/02)
General methods for inverting the stereochemistry of vinyl tertiary-alcohols such as 2 and 5 into 3 and 8 respectively are described.The procedures employ a sulfoxide rearrangement and will facilitate the extended use of the oxy-Cope rearrangement to a variety of related ring systems.
