A Synthetic Study of Chiral α-Hydroxy-H-Phosphinates Based on Proline Catalysis

Authors

  • Qiuli Yao,

    1. 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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  • Prof. Dr. Chengye Yuan

    Corresponding author
    1. 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
    • 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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