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Rhodium-Catalyzed Enantioselective Synthesis,Structures, and Properties of Single and Double Azahelicene-Like Molecules |
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| Authors: | Kyoichi Hanada Juntaro Nogami Prof?Dr Kazunori Miyamoto Norihiko Hayase Dr Yuki Nagashima Yusuke Tanaka Dr Atsuya Muranaka Prof?Dr Masanobu Uchiyama Prof?Dr Ken Tanaka |
| Institution: | 1. Department of Chemical Science and Engineering, Tokyo Institute of Technology O-okayama, Meguro-ku, Tokyo, 152-8550 Japan;2. Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033 Japan;3. Advanced Elements Chemistry Laboratory, Cluster for Pioneering Research (CPR), RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198 Japan;4. Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033 Japan
Advanced Elements Chemistry Laboratory, Cluster for Pioneering Research (CPR), RIKEN, 2-1 Hirosawa, Wako, Saitama, 351-0198 Japan |
| Abstract: | The enantioselective synthesis of aza6] and 7]helicene-like molecules have been achieved by the cationic rhodium(I)/axially chiral biaryl bisphosphine complex-catalyzed intramolecular 2+2+2] cycloaddition of cyanodiynes. This protocol was successfully applied to the diastereo- and enantioselective synthesis of an S-shaped double aza6]helicene-like molecule with a high ee value of 89 %. Although no epimerization and racemization were observed in the double carbo6]helicene-like molecule at 80 °C, epimerization and racemization of the double aza6]helicene-like molecule proceeded at 80 °C. This double aza6]helicene-like molecule showed good fluorescent quantum yields and chiroptical responses under both neutral and acidic conditions. |
| Keywords: | asymmetric catalysis azahelicene-like molecules cyanodiynes [2+2+2] cycloaddition circularly polarized luminescence |