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Synthesis of l-Selenocysteine and α-Methyl-l-Selenocysteine Derivatives Using Woollins’ Reagent and Their Application as Chiral Selenium Catalysts

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Abstract

The reaction of oxazolines, which were synthesized from l-serine methyl ester, with Woollins’ reagent in refluxing acetonitrile for 2 h and subsequent treatment of the crude products with sodium borohydride gave l-selenocysteine derivatives in up to 82 % yield without occurring racemization. Similar reaction protocols were applied for α-methyl-l-serine derivatives to afford various optically pure α-methyl-l-selenocysteine derivatives in moderate yields (~43 %). The obtained α-methylselenocysteine derivatives were applied as a catalyst for asymmetric cyclization of β,γ-unsaturated acids to α,β-unsaturated lactones in the presence of ammonium persulfate. The highest optical yield (27 % e.e.) was achieved when N,N′-diacetyl-α,α′-dimethyl-l-selenocystine diethyl ester was employed as a catalyst. Thus, potential usability of selenoamino acid derivatives as chiral organoselenium catalysts was demonstrated.

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Scheme 1
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Acknowledgments

The authors thank Ajinomoto Company, Japan, for proving us α-methyl-l-serine. This work was supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan (Grant-in-Aid for Scientific Research(C) no. 23550198).

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Authors and Affiliations

  1. Department of Chemistry, School of Science, Tokai University, Kitakaname, Hiratsuka-Shi, Kanagawa, 259-1292, Japan

    Michio Iwaoka, Shun Ito, Izumo Miyazaki & Momoko Michibata

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  1. Michio Iwaoka
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  2. Shun Ito
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Correspondence to Michio Iwaoka.

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Iwaoka, M., Ito, S., Miyazaki, I. et al. Synthesis of l-Selenocysteine and α-Methyl-l-Selenocysteine Derivatives Using Woollins’ Reagent and Their Application as Chiral Selenium Catalysts. Proc. Natl. Acad. Sci., India, Sect. A Phys. Sci. 86, 499–509 (2016). https://doi.org/10.1007/s40010-016-0307-8

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