Mislow-Evans rearrangement, and

Scheme 18.SB Condensation of a chiral bis-sulfoxide with cyclopentanone followed by a double Mislow-Evans rearrangement and ketones.—...

During the final stages of the total synthesis of (-)-subergorgic acid by L.A. Paquette and co-workers, the transposition of a tricyclic enone was needed. The enone was exposed to the Luche conditions and an 85 15 mixture of diastereomers was obtained. In order to achieve this level of diastereoselectivity, the reaction temperature had to be lowered to -50 °C instead of the usual 0 °C. The major product was formed via the exo attack of the carbonyl group by the hydride. The allylic alcohol was later converted to the corresponding sulfoxide followed by a Mislow-Evans rearrangement to the isomeric allylic alcohol. 

The first asymmetric total synthesis of the macrocyclic lactone metabolite (+)-pyrenolide D was accomplished in the laboratory of D.Y. Gin. The natural product has a densely functionalized polycyclic structure and its absolute configuration had to be established. The key step of the synthesis was a stereoselective oxidative ring-contraction of a 6-deoxy-D-gulal, which was prepared from anomeric allylic sulfoxide via the Mislow-Evans rearrangement. 

The Mislow-Evans rearrangement was chosen by T. Tanaka and co-workers to create the C12 stereocenter of halicholactone and ensure the ( ) stereochemistry of the C9-C11 double bond. ... 

Jones-Hertzog, D. K., Jorgensen, W. L. Elucidation of Transition Structures and Solvent Effects for the Mislow-Evans Rearrangement of Allylic Sulfoxides. J. Am. Chem. Soc. 1995, 117, 9077-9078. 

Claisen, Carrol rearrangement, Eschenmoser-Claisen, Johnson-Claisen and Ireland-Claisen rearrangements/Mislow-Evans rearrangement... 

Scheme 18.23 Oxidant for pseudothioglycal oxidation varies with protecting groups (Danishefslw. 1991 Rojas. 2001 and application of Mislow-Evans rearrangement with a galactal-derived 4-hydroxy-6-deoxy derivative.—...

Scheme 18.40 Regioselective additions of metallated sulfinyl pentadienyl anions to ketones or aldehydes and double Mislow-Evans rearrangement.—...

This chapter is organized by theme rather than chronologically, and while the most recent applications certainly highlight the continuing significance of the Mislow-Evans rearrangement in synthesis endeavors, classic exanples are also included to paint a full picture of the reaction s significance and as a source of inspiration for contenporary practitioners of our art. 

More recently, calculations on a variety of [2,3]-rearrangement transition states, including that for the Mislow-Evans rearrangement, highlighted the electron-delocalized aromatic character of the transition states (e.g., 36 Scheme 18.111. befitting concerted processes. The magnetic character of the transition states was also computed and found to be consistent with their having an aromatic nature. ... 

Alkylation of an allylic sulfoxide followed by Mislow-Evans rearrangement was particularly facile within a cyclic system. Deprotonation and methylation of cyclohexenyl substrate 126 led to the a,a-disubstituted allyl sulfoxide 127, which rearranged readily under mild conditions, perhaps aided by relief of steric crowding. Trimethylphosphite was employed as the thiophile, providing the allylic alcohol 128, the overall equivalent of methylation of a 3-hydroxycyclohexenyl vinyl anion.(Scheme 1R.36E... 

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