Title:
OPTICALLY ACTIVE QUATERNARY AMMONIUM SALT, PROCESS FOR PRODUCING THE SAME, AND PROCESS FOR PRODUCING OPTICALLY ACTIVE alpha-AMINO ACID DERIVATIVE WITH THE SAME
Document Type and Number:
WIPO Patent Application WO2005007622
Kind Code:
A3
Abstract:
[PROBLEMS] To provide (1) an optically active quaternary ammonium salt which, when used as an asymmetric-axis-containing spiro type phase-transfer catalyst for the asymmetric alkylation of a glycine derivative, shows high stereoselectivity for substrates such as ones having a small molecular size, e.g., methyl iodide, and sec-alkyl halides; an optically active alpha-amino acid derivative produced stereroselectively and useful as an intermediate for medicines and agricultural chemicals; and a process for producing the derivative; and (2) a novel optically active quaternary ammonium salt which has high performance when used as an asymmetric-axis-containing spiro type phase-transfer catalyst for the asymmetric alkylation of a glycine derivative, and in which the rings constituting the spiro skeleton have the same structure, which is advantageous from the standpoint of the number of catalyst synthesis steps; a process for producing the salt; and a method of recovering the salt. [MEANS FOR SOLVING PROBLEMS] (1) An asymmetric-axis-containing spiro type ammonium salt having an alkyl- or aryl-substituted silyl group introduced on an aromatic ring is used as a phase-transfer catalyst to conduct the asymmetric alkylation of a glycine derivative. (2) An asymmetric-axis-containing spiro type ammonium salt having introduced therein a substituent including a perfluoroalkyl group is used in the asymmetric alkylation of a glycine derivative and then recovered with a fluorous solvent.
Inventors:
MARUOKA KEIJI (JP)
Application Number:
PCT/JP2004/010387
Publication Date:
March 31, 2005
Filing Date:
July 22, 2004
Export Citation:
Assignee:
TOSOH CORP (JP)
MARUOKA KEIJI (JP)
MARUOKA KEIJI (JP)
International Classes:
B01J31/02; B01J31/28; C07C249/02; C07C251/24; C07D487/10; C07F7/08; C07F7/10; C07F7/12; C07B53/00; C07D; (IPC1-7): C07F7/10; B01J31/02; B01J31/28; C07C249/02; C07C251/24; C07D487/10; C07F7/08; C07F7/12
Foreign References:
| JP2002356454A | 2002-12-13 |
Other References:
OOI T. ET AL.: "Design of N-spiro C2-symmetric chiral quternary ammonium bromides as novel phase-transfer catalysts: synthesis and application to practitcal asymmetric synthesis of alpha-amino acids", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 125, no. 17, 2003, pages 5139 - 5151, XP002986337
MAILLARD D. ET AL.: "Chiral perfluorous analogues of MOP. synthesis and applications in catalysis", TETRAHEDRON: ASYMMETRY, vol. 13, no. 13, 2002, pages 1449 - 1456, XP004374321
YAMASHITA Y. ET AL.: "Highly anti-selective asymmetric aldol reactions using chiral zirconium catalysts. Improvement of activities, structure of the novel zirconium complexes, and effect of a small amount of water for the preparation of the catalysts", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 124, no. 13, 2002, pages 3292 - 3302, XP001103973
TIAN Y. ET AL.: "An asymmetric catalytic carbon-carbon bond formation in a fluorous biphasic system based on perfluoroalkyl-BINOL", TETRAHEDRON LETTERS, vol. 41, no. 45, 2000, pages 8813 - 8816, XP004236084
See also references of EP 1650212A4
MAILLARD D. ET AL.: "Chiral perfluorous analogues of MOP. synthesis and applications in catalysis", TETRAHEDRON: ASYMMETRY, vol. 13, no. 13, 2002, pages 1449 - 1456, XP004374321
YAMASHITA Y. ET AL.: "Highly anti-selective asymmetric aldol reactions using chiral zirconium catalysts. Improvement of activities, structure of the novel zirconium complexes, and effect of a small amount of water for the preparation of the catalysts", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 124, no. 13, 2002, pages 3292 - 3302, XP001103973
TIAN Y. ET AL.: "An asymmetric catalytic carbon-carbon bond formation in a fluorous biphasic system based on perfluoroalkyl-BINOL", TETRAHEDRON LETTERS, vol. 41, no. 45, 2000, pages 8813 - 8816, XP004236084
See also references of EP 1650212A4
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