A study on the substituent effects of norbornadiene derivatives in iridium-catalyzed asymmetric [2 + 2] cycloaddition reactions.

Jun Hu, Qingjing Yang, Lu Yu, Jianbin Xu, Shanshan Liu, Chao Huang, Lin Wang, Yongyun Zhou, Baomin Fan

Key Laboratory of Chemistry in Ethnic Medicinal Resources, State Ethnic Affairs Commission and Ministry of Education, Yunnan University of Nationalities, Kunming, 650500, China.

Organic & biomolecular chemistry 2013 Apr 14

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Employing a series of norbornadiene derivatives as substrates, the effects of various substituents on the Ir-catalyzed asymmetric [2 + 2] cycloaddition reactions with arylacetylenes were studied. It was found that the atom forming the short bridge chain had a great effect on the enantioselectivity of the reaction. Heteroatoms, such as oxygen and nitrogen, always resulted in excellent enantioselectivity. However, carbon atoms could decrease the enantioselective control ability of the catalyst over the reaction. The groups on the unreacted carbon-carbon double bond were found to have but a little effect on the reaction. Based on the results of the experiments, a mechanism was also hypothesized for the reaction.

Citation

Jun Hu, Qingjing Yang, Lu Yu, Jianbin Xu, Shanshan Liu, Chao Huang, Lin Wang, Yongyun Zhou, Baomin Fan. A study on the substituent effects of norbornadiene derivatives in iridium-catalyzed asymmetric [2 + 2] cycloaddition reactions. Organic & biomolecular chemistry. 2013 Apr 14;11(14):2294-301