Diastereoselective Allylations Of Enantiopure 3- And 4-Substituted Eta(4)-(1z)-(Sulfinyldienal)Iron(0) Tricarbonyl Complexes

Diastereoselectivity of allylations of enantiopure 3- and 4-substituted eta(4)-(1Z)-(sulfinyldienal)iron(0) tricarbonyl complexes is dependent on the nature of the alkyl substituent. For 1-sulfinyl-1,3-pentadien-5-al iron complexes (11a-d), the aldehyde predominately reacts through the s-cis conformer, with diastereoselectivites as high as 95:5 (for homoallylic alcohol 13d). For 3-formyl-1-sulfinyl-1,3-butadiene iron complexes (12a,b), the aldehyde predominately reacts through the s-trans conformer (diastereomer ratio for homoallylic alcohol, 14b, 89:11)

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)-(1Z)-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