This report describes a new Pd-catalyzed oxidation reaction for the stereospecific conversion of enynes into cyclopropyl ketones. Unlike related PdII/0, Au, and Pt-catalyzed cyclopropane-forming reactions, these transformations proceed with net inversion of geometry with respect to the starting olefin. This result is consistent with a PdII/IV mechanism in which the key cyclopropane-forming step involves nucleophilic attack of a tethered olefin onto the PdIV−C bond.

The development of porous functional materials, using template copolymerization, that function in gas binding/release and catalysis is described. Using substitutionally inert metal complexes as templates, materials were prepared with immobilized sites that retained structural properties of the template; this allows for tunable functional properties. Chemical modification of the immobilized sites led to coordinatively unsaturated metal centers that reversibly bind either O2 or NO. Materials have also been prepared that exhibit varying degrees of catalytic activity in the hydrolytic kinetic resolution of epoxides as a function of the template concentration used to prepare the polymers.

Template copolymerization methods have been utilized to prepare porous materials with immobilized cobalt complexes that catalyze the hydrolytic kinetic resolution of epoxides.

Synthesis of Cyclopropanes via Pd(II)/(IV)-Catalyzed Reactions of Enynes. -Diverse bicyclo[3.1.0] and [4.1.0] ring systems containing lactones, tetrahydrofurans, pyrrolidines, and lactams are prepared by palladium(II/IV) catalyzed cascade cyclizations of enynes. Aryl and alkyl substitutions are well tolerated. Cyclopropane formation proceeds with clean inversion of the starting olefin geometry; however side products can be formed from the Pd intermediates during the cyclopropane-forming pathway. -(WELBES, L. L.; LYONS, T. W.; CYCHOSZ, K. A.; SANFORD*, M. S.; J. Am.

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