Formal Umpolung Addition of Phosphites to 2-Azaaryl Ketones under Chiral Brønsted Base Catalysis: Enantioselective Protonation Utilizing [1,2]-Phospha-Brook Rearrangement |
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Authors: | Prof?Dr Azusa Kondoh Takayuki Hirozane Prof?Dr Masahiro Terada |
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Institution: | 1. Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University Aramaki, Aoba-ku, Sendai, 980-8578 Japan;2. Department of Chemistry, Graduate School of Science, Tohoku University Aramaki, Aoba-ku, Sendai, 980-8578 Japan |
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Abstract: | The formal enantioselective umpolung addition of dialkyl phosphites to 2-azaaryl ketones was developed under Brønsted base catalysis. The reaction involves the enantioselective protonation of the transient α-oxygenated (2-azaaryl)methyl anion generated through the 1,2-addition of the anion of dialkyl phosphite to the 2-azaaryl ketone and the subsequent 1,2]-phospha-Brook rearrangement. A chiral bis(guanidino)iminophosphorane organosuperbase efficiently catalyzed the reaction to provide enantio-enriched phosphates in high yields with good to high enantioselectivities. This is a rare example of the catalytic enantioselective protonation of transient carbanions other than enolates, constructing a trisubstituted stereogenic center α to 2-azaarenes. |
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Keywords: | enantioselective protonation organocatalysis organosuperbase phospha-Brook rearrangement umpolung |
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