Title:
METHOD FOR INTRODUCING SUBSTITUENTS INTO α,β-UNSATURATED KETONE AND PROSTAGLANDIN COMPOUND SYNTHESIS METHOD UTILIZING SAME
Document Type and Number:
WIPO Patent Application WO/2019/026402
Kind Code:
A1
Abstract:
[Problem] To provide a method for introducing substituents into an α,β-unsaturated ketone and a prostaglandin compound synthesis method utilizing said method, the former method being for introducing substituents into the α-position and β-position of the α,β-unsaturated ketone, being utilizable for synthesizing a prostaglandin compound by a three-component linking method, and being capable of synthesizing a desired compound in high yield through a one-pot operation without requiring any of the three ingredients necessary for the synthesis to be used in large excess and without using any highly toxic heavy metal as a catalyst or using any solvent highly toxic to the living body.
[Solution] The method for introducing substituents into an α,β-unsaturated ketone of the present invention is for introducing substituents onto the α-position carbon atom and β-position carbon atom of the α,β-unsaturated ketone, and is characterized by comprising a first step, in which an alkyllithium is mixed with a trialkylalkenyltin in which the tin atom has been bonded to the vinyl-position of the alkenyl group, a second step, in which the mixture obtained in the first step is mixed with a dialkylzinc, a third step, in which the mixture obtained in the second step is mixed with the α,β-unsaturated ketone, and a fourth step, in which the mixture obtained in the third step is mixed with a trifluoromethanesulfonate compound.
Inventors:
SUZUKI MASAAKI (JP)
KOYAMA HIROKO (JP)
KOYAMA HIROKO (JP)
Application Number:
PCT/JP2018/020527
Publication Date:
February 07, 2019
Filing Date:
May 29, 2018
Export Citation:
Assignee:
NAT CT GERIATRICS & GERONTOLOGY (JP)
International Classes:
C07F7/18; C07C405/00
Other References:
SUZUKI, M. ET AL.: "Three-component coupling synthesis of prostaglandins a simplified general procedure", TETRAHEDRON, vol. 46, no. 13-14, 1 January 1990 (1990-01-01), pages 4809 - 4822, XP055679011
GOODING, 0. W. ET AL.: "Triply Convergent Synthesis of 15-(Phenoxymethyl) and 4,5-Allenyl Prostaglandins. Preparation of an Individual Isomer of Enprostil1", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 58, 1993, pages 3681 - 3686, XP002386527
CHEN, H. -J. ET AL.: "Expeditious Entry to the Chamigrane Endoperoxide Family of Natural Products", ORGANIC LETTERS, vol. 17, no. 3, 2015, pages 592 - 595, XP055678565, DOI: 10.1021/ol503603t
HOLEC, C. ET AL.: "Chemoenzymatic Synthesis towards the Active Agent Travoprost", CHEMCATCHEM, vol. 7, 31 August 2015 (2015-08-31), pages 3125 - 3130, XP055679016, ISSN: 1867-3880 , DOI: 10.1002/cctc.201500587
LIPSHUTZ, B. H. ET AL.: "A Practical, General Three-Component Coupling Approach to Prostaglandin and Non-Prostaglandin-Related Skeleta", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 116, no. 26, 1994, pages 11689 - 11702, XP055678567, DOI: 10.1021/ja00105a010
SUZUKI, M.YANAGISAWA, A.NOYORI, R., J. AM. CHEM. SOC., vol. 107, 1985, pages 3348 - 3349
SUZUKI, M.YANAGISAWA, A.NOYORI, R., J. AM. CHEM. SOC., vol. 110, 1988, pages 4718 - 4726
MORITA, Y.SUZUKI, M.NOYORI, R., J. ORG. CHEM., vol. 54, 1989, pages 1785 - 1787
SUZUKI, M.MORITA, Y.KOYANO, H.KOGA, M.NOYORI, R., TETRAHEDRON, vol. 46, 1990, pages 4809 - 4822
SUZUKI, M.KATO, K.NOYORI, R.WATANABE, Y.TAKECHI, H.MATSUMURA, K.LANGSTRORN, B.WATANABE, Y., ANGEW. CHEM., INT. ED. ENG., vol. 35, 1996, pages 334 - 336
SUZUKI, M.KATO, K.WATANABE, YSATOH. T.MATSUMURA, K.WATANABE, YNOYORI, R., CHEM. COMMUN., 1999, pages 307 - 308
SUZUKI, M.DOI, H.HOSOYA, T.LANGSTROM, B.WATANABE, Y., TRENDS ANAL. CHEM, vol. 23, 2004, pages 595 - 607
See also references of EP 3663305A4
GOODING, 0. W. ET AL.: "Triply Convergent Synthesis of 15-(Phenoxymethyl) and 4,5-Allenyl Prostaglandins. Preparation of an Individual Isomer of Enprostil1", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 58, 1993, pages 3681 - 3686, XP002386527
CHEN, H. -J. ET AL.: "Expeditious Entry to the Chamigrane Endoperoxide Family of Natural Products", ORGANIC LETTERS, vol. 17, no. 3, 2015, pages 592 - 595, XP055678565, DOI: 10.1021/ol503603t
HOLEC, C. ET AL.: "Chemoenzymatic Synthesis towards the Active Agent Travoprost", CHEMCATCHEM, vol. 7, 31 August 2015 (2015-08-31), pages 3125 - 3130, XP055679016, ISSN: 1867-3880 , DOI: 10.1002/cctc.201500587
LIPSHUTZ, B. H. ET AL.: "A Practical, General Three-Component Coupling Approach to Prostaglandin and Non-Prostaglandin-Related Skeleta", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 116, no. 26, 1994, pages 11689 - 11702, XP055678567, DOI: 10.1021/ja00105a010
SUZUKI, M.YANAGISAWA, A.NOYORI, R., J. AM. CHEM. SOC., vol. 107, 1985, pages 3348 - 3349
SUZUKI, M.YANAGISAWA, A.NOYORI, R., J. AM. CHEM. SOC., vol. 110, 1988, pages 4718 - 4726
MORITA, Y.SUZUKI, M.NOYORI, R., J. ORG. CHEM., vol. 54, 1989, pages 1785 - 1787
SUZUKI, M.MORITA, Y.KOYANO, H.KOGA, M.NOYORI, R., TETRAHEDRON, vol. 46, 1990, pages 4809 - 4822
SUZUKI, M.KATO, K.NOYORI, R.WATANABE, Y.TAKECHI, H.MATSUMURA, K.LANGSTRORN, B.WATANABE, Y., ANGEW. CHEM., INT. ED. ENG., vol. 35, 1996, pages 334 - 336
SUZUKI, M.KATO, K.WATANABE, YSATOH. T.MATSUMURA, K.WATANABE, YNOYORI, R., CHEM. COMMUN., 1999, pages 307 - 308
SUZUKI, M.DOI, H.HOSOYA, T.LANGSTROM, B.WATANABE, Y., TRENDS ANAL. CHEM, vol. 23, 2004, pages 595 - 607
See also references of EP 3663305A4
Attorney, Agent or Firm:
AOYAMA Yo (JP)
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