Rhodium(I)-Catalyzed [2+2+2+2] Cycloaddition of Diynes To Form Cyclooctatetraenes

UNCG Author/Contributor (non-UNCG co-authors, if there are any, appear on document)
Mitchell Croatt, Assistant Professor (Creator)
The University of North Carolina at Greensboro (UNCG )
Web Site: http://library.uncg.edu/

Abstract: Unique reactivity of a rhodium catalyst in the presence of many different Lewis basic additives was observed and studied. In the absence of additives, it was observed that a selective [2+2+2] reaction to form benzene products occurred; however, in the presence of an additive, optimally DMSO, the first rhodium(I)-catalyzed [2+2+2+2] reaction of alkynes occurred. A screen of different additives and catalysts was performed. Finally, a brief mechanistic study per-formed by using a ReactIR determined that DMSO coordinates to the catalyst, which affects the energetics of the reaction pathway. This appears primarily to raise the transition-state energy for the reductive elimination to form the benzene products.

Additional Information

European Journal of Organic Chemistry 2014, 2014, 3767-3772
Language: English
Date: 2014
Organometallics, Cycloaddition, Alkynes, Nickel, Rhodium

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