Asymmetric Allylic Monofluoromethylation and Methylation of Morita–Baylis–Hillman Carbonates with FBSM and BSM by Cooperative Cinchona Alkaloid/FeCl2 Catalysis


  • This study was financially supported in part by Grants-in-Aid for Scientific Research (21390030, 22106515, Project No. 2105: Organic Synthesis Based on Reaction Integration). We also thank TOSOH F-TECH INC. and the Asahi Glass Foundation. FBSM=fluorobis(phenylsulfonyl)methane, BSM=bis(phenylsulfonyl)methane.


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Working together: The title reactions were achieved in high yields with high ee values (see scheme, (DHQD)2AQN=hydroquinidine(anthraquinone-1,4-diyl) diether). The cooperative catalysis of bis(cinchona alkaloid) and Lewis acid, particularly FeCl2, was effective for these transformations and gave the monofluoromethylation products with over 90 % ee and methylation products with up to 97 % ee.