I. Catalytically active and recyclable zirconocene functionalized polymeric disks. II. Solid phase and solution phase synthesis of 2-arylcycloalka-2,4-dienone derivatives employing 1-phenylsulfanyl)methylphenylsulfone

I. We achieved the synthesis of the first example (to our knowledge) of a polymerizable zirconocene dichloride and incorporated the zirconocene dichloride unit at a cross-link between polymer chains. Co-polymerization of bis(4-vinylbenzylcyclopentadienyl)zirconium dichloride and styrene in a test tube, followed with extraction of the polymer rod and slicing into 'disks' 1--3 mm thick and 5 mm in diameter gave the supported zirconocene species that exhibited both stoichiometric and catalytic activity. The disks catalyzed reaction of trimethylaluminium and phenylacetylene to give alpha-methylstyrene with modest turnover numbers and are active over at least six recyclings. We have demonstrated that polymerization of an otherwise sensitive organometallic can give rise to polymer-bound species exhibiting both catalytic activity and recyclability.; II. The use of 1-(phenylsulfanyl)methylphenylsulfone in solution phase synthesis has shown great versatility in the preparation of a small library of 2 arylcycloalka-2,4-dienone derivatives. The reaction sequence of 1-(phenylsulfanyl)methylphenylsulfone carbanion addition to alkenyl aryl ketones, followed with Trost's protocol for 1,2-aryl migration, regioselective allylation, Grubbs' ruthenium catalyzed ring closing metathesis, and finally oxidation and dehydrosulfenylation gave 2-arylcycloalka-2,4-dienones with modest to excellent yields. The syntheses demonstrate high potential for adaptation of the methodology to solid phase combinatorial synthesis. Solid phase organic synthesis of the 2-arylcycloalka-2,4-dienones employing 1-(phenylsulfanyl)methylphenylsulfone substrates is currently under experimental investigation.