Synthesis and Diastereoselective Complexation of Enantiopure Sulfinyl Dienes: The Preparation of Sulfinyl Iron(0) Dienes

The preparation of a diverse array of enantiomerically pure 1- and 2-sulfinyl dienes has been achieved via Stille coupling of halovinyl sulfoxides and vinyl stannanes, hydrogenation of 1-sulfinyl-1-en-3-ynes, or vinylcupration of 1-sulfinyl alkynes. Formation of the corresponding sulfinyl diene iron(0) tricarbonyl complexes was accomplished by utilizing Fe(CO) 5 /NMO or (bda)Fe(CO) 3 as iron(0) tricarbonyl transfer reagents. Installation of the iron(0) tricarbonyl fragment was shown to be highly diastereoselective (10−16:1) for ( R )-(1 Z )-1-sulfinyl dienes, most likely as a result of allylic 1,3-strain. The synthesis of a 1-sulfinyl-1,3,8,10-tetraene is also described.