Stereoselective Functionalization of Dihydropyran‐3‐ols: Application to the Synthesis of Enantiopure Ethyl Deoxymonate B

The behavior of readily available enantiopure cis and trans 3,6‐disubstituted dihydropyran‐3‐ols and derivatives in epoxidation, osmium‐catalyzed dihydroxylations, SN2′, and Claisen‐related processes has been examined. The highly diastereoselective dihydroxylation of a suitably functionalized cis 3,6‐disubstituted dihydropyran‐3‐ol has been used in the synthesis of ethyl deoxymonate B from a 3‐sulfinyldihydropyran intermediate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) Selective dihydroxylation of a dihydropyranol and a cross‐metathesis reaction are the key steps in the synthesis of an enantiopure ethyl deoxymonate B from a sulfinyl dienol.