Method of enantioselective nucleophilic addition reaction of...

Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters

Reexamination Certificate

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C560S032000, C560S157000, C560S160000, C560S163000, C560S336000, C560S346000, C548S400000, C548S543000, C549S295000, C549S313000

Reexamination Certificate

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07414145

ABSTRACT:
A method of an enantioselective nucleophilic addition reaction to carbonyl, which enables an asymmetric synthesis of an optically active α-hydroxy-γ-keto acid ester, an optically active α-hydroxy-γ-amino acid ester, hydroxydiketone compounds, etc. being useful as a raw material or synthesis intermediate for producing a pharmaceutical preparation, an agricultural chemical, a fragrance, a functional polymer or the like. In this method, the nucleophilic addition reaction of enamide compound accompanied by hydroxyl (—OH) formation to carbonyl is carried out in the presence of a chiral catalyst with copper or nickel.

REFERENCES:
patent: 2003-260363 (2003-09-01), None
patent: 2003-260366 (2003-09-01), None
Ryosuke Matsubara, Yoshitaka Nakamura and Shu kobayashi Angew. Chem. Int. Ed. 2004, 43, 3258-3260.
Ryosuke Matsubara et al., “Copper(II)-Catalyzed Highly Enantioselective Addition of Enamides to Imines: The Use of Enamides as Nucleophiles in Asymmetric Catalysis”, Angew. Chem. Int. Ed., 43, pp. 1679-1681, 2004.
Yoshitaka Nakamura et al. “Catalytic, Asymmetric Mannich-Type Reactions of α-Imino Esters Bearing Readily Removable Substituents on Nitrogen”, Organic Letters, vol. 5, No. 14, pp. 2481-2484, 2003.
Shü Kobayashi et al., “Catalytic, Asymmetric Mannich-Type Reactions ofN-Acylimino Esters for Direct Formation ofN-Acylated Amino Acid Derivatives. Efficient Synthesis of a Novel Inhibitor of Ceramide Trafficking, HPA-12” Organic Letters, vol. 4, No. 1, pp. 143-145, 2002.
Shü Kobayashi et al., “Catalytic Asymmetric Synthesis of α-Amino Phosphonates Using Enantioselective Carbon Carbon Bond-Forming Reactions”, J. Am. Chem. Soc., 126, pp. 6558-6559, 2004.
Ryosuke Matsubara et al., “Highly Diastereo- and Enantioselective Reactions of Enecarbamates with Ethyl Glyoxylate to Give Optically Activesynandantiα-Alkyl-β-Hydroxy Imines and Ketones”, Angew. Chem. Int. Ed., 43, 3258-3260, 2004.
Ryosuke Matsubara et al., “Highly diastereo- and enantioselective reactions of enecarbamates with an aldehyde”, Tetrahedron, 60, pp. 9769-9784, 2004.
Ryosuke Matsubara et al., “Development of Catalytic Asymmetric Reactions Using Enamides as Nucleophiles”, The Chemical Society of Japan, p. 1220, Mar. 11, 2004.

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