[2,3]-Sigmatropic rearrangement of propargylic sulfinates ; Regiodivergent synthesis of 1- and 2 arylsulfonyl 1,3-dienes, and III. Synthesis of Troger's base-derived ligands
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[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT AUTHOR'S REQUEST.] The [2,3]-sigmatropic rearrangement of propargylic sulfinates to allenic sulfones was studied under both silver and copper catalysis. Metal salts having non-coordinating anions were effective at promoting the rearrangement. In addition, recoverable and reusable metal-doped ultrastable Y (USY) zeolites are able to catalyze the rearrangement, making the process more environmentally "green". In the course of studying some organometallic chemistry of allenic sulfones, we discovered a facile palladium-catalyzed isomerization of these species to 1-arylsulfonyl 1,3-dienes. In the absence of palladium, but in the presence of a nucleophile and proton shuttle, such allenes can be converted to 2-arylsulfonyl 1,3-dienes. The mechanisms of both processes are examined. Troger?s base is a non-natural chiral amine whose analogues have applications in many areas. The sterics of Troger?s base prevent it from functioning as a bidentate ligand. We have designed a ligand derived from the Troger?s base structural framework that is dianionic and contains multiple coordination sites for transition metal and actinide complexation.
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