Title:
METHOD FOR PRODUCING OPTICALLY ACTIVE FLUORINE-CONTAINING OXETEN
Document Type and Number:
WIPO Patent Application WO/2012/070437
Kind Code:
A1
Abstract:
[Problem] To provide a practical production method by which an optically active fluorine-containing oxeten, which can be an important intermediate for pharmaceuticals and agrochemicals, is able to be stably isolated.
[Solution] This method for producing an optically active fluorine-containing oxeten is characterized in that a fluorine-containing α-ketoester and an internal alkyne are caused to react with each other in the presence of a transition metal complex that has an optically active ligand.
By adopting the production method of the present invention, an optically active fluorine-containing oxeten can be obtained with high regioselectivity and high stereoselectivity (high optical purity) with high yield even in cases where the amount of an asymmetric catalyst is relatively low. In addition, the thus-obtained optically active fluorine-containing oxeten can be converted into various useful intermediates.
Inventors:
MIKAMI KOICHI
AIKAWA KOHSUKE
HIOKI YUTA
AIKAWA KOHSUKE
HIOKI YUTA
Application Number:
PCT/JP2011/076359
Publication Date:
May 31, 2012
Filing Date:
November 16, 2011
Export Citation:
Assignee:
TOKYO INST TECH (JP)
CENTRAL GLASS CO LTD (JP)
MIKAMI KOICHI
AIKAWA KOHSUKE
HIOKI YUTA
CENTRAL GLASS CO LTD (JP)
MIKAMI KOICHI
AIKAWA KOHSUKE
HIOKI YUTA
International Classes:
C07D305/10; C07B61/00; C07D407/04; C07D409/04
Foreign References:
| JP2010222345A | 2010-10-07 | |||
| JP2010195736A | 2010-09-09 |
Other References:
MAIER,G. ET AL.: "Small rings. 88. Reactions of tetra-tert-butyl-tetrahedrane: oxidation to the radical cation as the first step", LIEBIGS ANNALEN 0947-3440, 1995, pages 161 - 167, XP055107673
OBLIN,M. ET AL.: "Experimental evidence for a [2 + 2] mechanism in the Lewis acid-promoted formation of a,p-unsaturated esters from ethoxyacetylene and aldehydes.Synthesis and characterization of 4-ethoxyoxetes", CHEMICAL COMMUNICATIONS, 1998, pages 1619 - 1620, XP055106839
LONGCHAR,M. ET AL.: "A convenient synthesis of oxetene via [2+2]cycloaddition reaction under microwave irradiation", SYNTHETIC COMMUNICATIONS, vol. 32, no. 23, 2002, pages 3611 - 3616, XP055106841
HAYASHI,A. ET AL.: "SbF5-Promoted Addition of Aldehydes to Alkynes", SYNLETT, 1995, pages 195 - 196, XP055106860
MIDDLETON,W.J. ET AL.: "Isolation of a cyclic intermediate in the ketone-alkoxyacetylene reaction", JOURNAL OF ORGANIC CHEMISTRY, vol. 30, no. 4, 1965, pages 1307, XP055106865
FRIEDRICH,L.E. ET AL.: "Detection of an oxetene intermediate in the photoreaction of benzaldehyde with 2-butyne", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 95, no. 20, 1973, pages 6869 - 6870, XP055106868
FRIEDRICH,L.E. ET AL.: "Photochemical preparation of a stable oxetene", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 91, no. 25, 1969, pages 7204 - 7205, XP055106870
FRIEDRICH,L.E. ET AL.: "Syntheses and Reactions of 3-Phenyloxete and the Parent Unsubstituted Oxete", JOURNAL OF ORGANIC CHEMISTRY, vol. 46, no. 2, 1981, pages 306 - 311, XP055106872
ADAM,W. ET AL.: "Dimethyldioxirane epoxidation of benzofurans: reversible thermal and photochemical valence isomerization between benzofuran epoxides, quinone methides, and benzoxetenes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 115, no. 19, 1993, pages 8603 - 8608, XP055106875
GOLUBEV, A.S ET AL.: "Carbonyl-yne reactions of 3,3,3-trifluoro-pyruvates", TETRAHEDRON, vol. 59, no. 9, 2003, pages 1389 - 1394, XP004409937
OBLIN,M. ET AL.: "Experimental evidence for a [2 + 2] mechanism in the Lewis acid-promoted formation of a,p-unsaturated esters from ethoxyacetylene and aldehydes.Synthesis and characterization of 4-ethoxyoxetes", CHEMICAL COMMUNICATIONS, 1998, pages 1619 - 1620, XP055106839
LONGCHAR,M. ET AL.: "A convenient synthesis of oxetene via [2+2]cycloaddition reaction under microwave irradiation", SYNTHETIC COMMUNICATIONS, vol. 32, no. 23, 2002, pages 3611 - 3616, XP055106841
HAYASHI,A. ET AL.: "SbF5-Promoted Addition of Aldehydes to Alkynes", SYNLETT, 1995, pages 195 - 196, XP055106860
MIDDLETON,W.J. ET AL.: "Isolation of a cyclic intermediate in the ketone-alkoxyacetylene reaction", JOURNAL OF ORGANIC CHEMISTRY, vol. 30, no. 4, 1965, pages 1307, XP055106865
FRIEDRICH,L.E. ET AL.: "Detection of an oxetene intermediate in the photoreaction of benzaldehyde with 2-butyne", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 95, no. 20, 1973, pages 6869 - 6870, XP055106868
FRIEDRICH,L.E. ET AL.: "Photochemical preparation of a stable oxetene", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 91, no. 25, 1969, pages 7204 - 7205, XP055106870
FRIEDRICH,L.E. ET AL.: "Syntheses and Reactions of 3-Phenyloxete and the Parent Unsubstituted Oxete", JOURNAL OF ORGANIC CHEMISTRY, vol. 46, no. 2, 1981, pages 306 - 311, XP055106872
ADAM,W. ET AL.: "Dimethyldioxirane epoxidation of benzofurans: reversible thermal and photochemical valence isomerization between benzofuran epoxides, quinone methides, and benzoxetenes", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 115, no. 19, 1993, pages 8603 - 8608, XP055106875
GOLUBEV, A.S ET AL.: "Carbonyl-yne reactions of 3,3,3-trifluoro-pyruvates", TETRAHEDRON, vol. 59, no. 9, 2003, pages 1389 - 1394, XP004409937
Attorney, Agent or Firm:
KOBAYASHI, Hiromichi et al. (JP)
Hiromichi Kobayashi (JP)
Hiromichi Kobayashi (JP)
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