Mislow—Evans rearrangement

Mislow-Evans Rearrangement (Evans (-Mislow) Rearrangement)... 

Scheme 42 Discovery of the Type K (Mislow-Evans) rearrangement...

Scheme 46 Deprenylation of lipopeptides by application of the Mislow-Evans rearrangement...

In a series of pubhcations Warren et al. demonstrated the usefulness of 1,3-chirality transfer in the context of Type M rearrangements to synthesize 1,4,5-stereo triads with -configured double bonds (Scheme 90) [209-211]. Based on their successful work on diol syntheses with 1,4-related stereogenic centers across E-configured double bonds [212,213] involving the Mislow-Evans rearrangement (Sect. 3.5), the authors developed a procedure for the stereoselective synthesis of E-homoallyhc sulfides. 

In the diterpene series a notable recent example of semisynthesis is that (ref.24) of pachiclavularolide (28) a substance isolated from the soft coral, Pachiclavularia violacea. starting from S-citronellal readily available from S-citronellol. The key step in the formation of the macrocycle is an intramolecular palladium-catalysed diyne cyclisation following initially a Mislow-Evans rearrangement of a sulphinyl ester from S-citronellal. ... 

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. ... 

Masaki, Y., Sakuma, K., Kaji, K. Facile synthesis of (E)-allylic alcohols by acid-catalyzed modification of the Mislow-Evans rearrangement of allylic sulfoxides. Chem. Pharm. Bull. 1985, 33, 2531-2534. 

Jones-Hertzog, D. K., Jorgensen, W. L. Regioselective Synthesis of Allylic Alcohols Using the Mislow-Evans Rearrangement A Theoretical Rationalization. J. Org. Chem. 1995, 60, 6682-6683. 

Table 3.6 Sequential Knoevenagel/Mislow-Evans rearrangement with various aldehydes catalysed by SiO2-(CH2)3-NEt2 (see Scheme 3.23).

The sulfoxide-sulfenate ester rearrangement (Mislow/Evans rearrangement) where the X-Y fragment is a sulfoxide. 

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

---