A Synthetic Study of Chiral α‐Hydroxy‐H‐Phosphinates Based on Proline Catalysis |
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Authors: | Qiuli Yao Prof. Dr. Chengye Yuan |
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Affiliation: | State Key Laboratory of Bio‐organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032 (P.R. China), Fax: (+86)?21‐5492‐5379 |
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Abstract: | A highly enantioselective synthesis of α‐hydroxyphosphinates was achieved based on the L ‐proline‐catalyzed aldol reaction of α‐acylphosphinates and acetone. Due to the preexisting chirality at the phosphorus center, mixtures of two diastereomers of the α‐hydroxyphosphinates were obtained in moderate to good yields, with simultaneously high enantioselectivity for both diastereomers. The products could be converted into α‐hydroxy‐H‐phosphinates with satisfactory yields. Furthermore, an unprecedented oxidation–reduction reaction of the α‐hydroxyphosphinates or α‐hydroxy‐H‐phosphinates to form phosphonates was observed, and the mechanism involved in such a chemical transformation is discussed. |
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Keywords: | aldol reactions asymmetric synthesis oxidation– reduction reactions phosphinates phosphonates |
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