Rhodium-Catalyzed [3+2+2] and [2+2+2] Cycloadditions of Two Alkynes with Cyclopropylideneacetamides†
Tomoka Yoshida
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Search for more papers by this authorYuki Tajima
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Search for more papers by this authorMasayuki Kobayashi
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Search for more papers by this authorKoji Masutomi
Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan) http://www.apc.titech.ac.jp/∼ktanaka/
Search for more papers by this authorProf. Dr. Keiichi Noguchi
Instrumentation Analysis Center, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Ken Tanaka
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan) http://www.apc.titech.ac.jp/∼ktanaka/
Japan Science and Technology Agency (JST), ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012 (Japan)
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)Search for more papers by this authorTomoka Yoshida
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Search for more papers by this authorYuki Tajima
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Search for more papers by this authorMasayuki Kobayashi
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Search for more papers by this authorKoji Masutomi
Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan) http://www.apc.titech.ac.jp/∼ktanaka/
Search for more papers by this authorProf. Dr. Keiichi Noguchi
Instrumentation Analysis Center, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Ken Tanaka
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)
Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8550 (Japan) http://www.apc.titech.ac.jp/∼ktanaka/
Japan Science and Technology Agency (JST), ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012 (Japan)
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588 (Japan)Search for more papers by this authorThis work was supported partly by a Grant-in-Aid for Scientific Research (No 25105714) from the the Ministry of Education, Culture, Sports, Science and Technology [MEXT (Japan)] and by ACT-C from the Japan Science and Technology Agency ]JST (Japan)]. We thank Takasago International Corporation for the gift of segphos and H8-binap, Umicore for generous support in supplying rhodium complexes, and Dr. Yu Shibata (Tokyo Institute of Technology) for assistance in the preparation of the manuscript.
Graphical Abstract
‘Cat nap’: The cationic RhI/H8-binap complex catalyzes the [3+2+2] cycloaddition of 1,6-diynes with cyclopropylideneacetamides to produce cycloheptadienes. In contrast, the cationic RhI/(S)-binap complex catalyzes the enantioselective [2+2+2] cycloaddition of terminal alkynes, acetylenedicarboxylates, and cyclopropylideneacetamides to produce spiro-cyclohexadienes.
Abstract
It has been established that a cationic rhodium(I)/H8-binap complex catalyzes the [3+2+2] cycloaddition of 1,6-diynes with cyclopropylideneacetamides to produce cycloheptadiene derivatives through cleavage of cyclopropane rings. In contrast, a cationic rhodium(I)/(S)-binap complex catalyzes the enantioselective [2+2+2] cycloaddition of terminal alkynes, acetylenedicarboxylates, and cyclopropylideneacetamides to produce spiro-cyclohexadiene derivatives which retain the cyclopropane rings.
Supporting Information
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