Sulfinyl‐Mediated Stereoselective Functionalization of Acyclic Conjugated Dienes

Abstract

The chemo‐ and stereocontrolled functionalization of conjugated sulfinyl dienes in a cascade process that involves a conjugate addition, diastereoselective protonation and a [2,3]‐sigmatropic rearrangement is reported. Enantioenriched 1,4‐diol and 1,4‐aminoalcohol derivatives are obtained in a very straightforward manner. Further functionalization of these structures, including highly stereoselective epoxidation, dihydroxylation and the stereodivergent synthesis of several polyols in a controlled fashion is described.

Base-Induced Sulfoxide-Sulfenate Rearrangement of 2-Sulfinyl Dienes for the Regio- and Stereoselective Synthesis of Enantioenriched Dienyl Diols

“…Spectroscopic data are in agreement with those previously reported. 17 (E) 8.68 mmol, yield: 73%. Spectroscopic data are in agreement with those previously reported.…”

“…2a In this context, during the last years, our group has developed the diastereoselective Michael-type addition to 1and 2-sulfinyl dienes (1 and 2) to generate transient allylic sulfoxides I that evolved through [2,3]-sigmatropic rearrange-ment (Scheme 1b). We have applied this tandem process intramolecularly for the stereoselective synthesis of enantiopure functionalized dihydropyrans 5 and tetrahydropyridinols 6 as well as intermolecularly for the synthesis of acyclic 2-ene-1,4-diols, 7 1,4-aminoalcohols, 8 and 1,4-hydroxysulfides 9 with a high degree of stereocontrol.…”