A mild and efficient isomerization/protonation sequence involving an appropriately functionalized indole precursor to generate a wide variety of pyran-fused indoles utilizing cooperative catalysis between cationic iridium (III) and bismuth triflate has been developed. Three distinct cyclization manifolds lead to bioactive scaffolds that can be obtained in good yields. In addition, N-substituted indoles can be synthesized enantioselectively via an oxocarbenium• chiral phosphate counterion strategy.

The reaction between cyclic carbonates and amines to produce hydroxyurethanes is an important alternative to current urethane chemistry. In order to address the issue of slow reaction rates, an efficient ring opening of cyclic carbonates with amines has been achieved utilizing cooperative catalysis. A new Lewis acid/Lewis base combination substantially decreases the reaction times for small molecule systems to reach complete conversion. Although triazabicyclodecene (TBD) has a substantial impact on the reaction rate, the addition of lithium triflate (LiOTf) as a co‐catalyst allows for the fastest ring opening reported in the current literature. Cooperative catalysis is also applied to the synthesis of polymers containing hydroxyurethane linkages and is able to achieve rapid conversion of the bis‐cyclic carbonate and diamine precursors when compared with the uncatalyzed reaction.

In Gemeinschaftsarbeit: Eine milde und effiziente Isomerisierungs‐Protonierungs‐Sequenz unter kooperativer Katalyse durch kationische Iridium(III)‐Spezies und Bi(OTf)3 ergibt Pyran‐anellierte Indole. Drei verschiedene Cyclisierungsarten führen in guten Ausbeuten zu den entsprechenden Gerüsten von biologisch aktiven Substanzen. In Gegenwart eines chiralen Phosphats sind auch N‐substituierte Indole enantioselektiv zugänglich.

The reaction between cyclic carbonates and amines to produce hydroxyurethanes is an important alternative to current urethane chemistry. In order to accelerate the reaction rate, a new efficient catalyst system is employed. This cooperative catalysis is also applied to the synthesis of polymers containing hydroxyurethane linkages. -(LOMBARDO, V. M.; DHULST, E. A.; LEITSCH, E. K.; WILMOT, N.; HEATH, W. H.; GIES, A. P.; MILLER, M. D.; TORKELSON*, J. M.; SCHEIDT, K. A.; Eur.

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