Title:
METHOD FOR PRODUCING NITROGEN-SELECTIVE CHIRAL ALDOL REACTION PRODUCT OF NITROSO COMPOUND USING ORGANIC CHIRAL CATALYST COMPOUND
Document Type and Number:
WIPO Patent Application WO/2024/034767
Kind Code:
A1
Abstract:
The present invention relates to a method for producing a chiral nitroso derivative using an organic chiral catalyst compound based on (R,R)-1,2-diphenylethylenediamine (DPEN), and the like. According to the production method, a chiral nitroso derivative with high enantioselectivity through an asymmetric aldol reaction between a cyclic ketone and a nitroso compound can be produced with high yield. In particular, in the production method of the present invention, the catalyst compound forms a hydrogen bond with the nitroso compound to activate an electrophile and form a transition state in such a manner that steric hindrance is minimized, thereby producing a stable product. In addition, a chiral nitroso derivative produced according to the present invention can be used in the main reaction of various synthetic intermediates, and thus can be used in the field of pharmaceutical organic synthesis.
Inventors:
SHIM JAE HO (KR)
KIM HYEON SOO (KR)
KIM HYEON SOO (KR)
Application Number:
PCT/KR2023/003846
Publication Date:
February 15, 2024
Filing Date:
March 23, 2023
Export Citation:
Assignee:
UNIV KOREA RES & BUS FOUND (KR)
International Classes:
C07C221/00; B01J31/02; C07C225/22
Foreign References:
| CN104860939A | 2015-08-26 |
Other References:
MOMIYAMA NORIE, YAMAMOTO HISASHI: "Brønsted Acid Catalysis of Achiral Enamine for Regio- and Enantioselective Nitroso Aldol Synthesis", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 127, no. 4, 1 February 2005 (2005-02-01), pages 1080 - 1081, XP093139954, ISSN: 0002-7863, DOI: 10.1021/ja0444637
MOMIYAMA NORIE, YAMAMOTO HISASHI: "Enantioselective O - and N -Nitroso Aldol Synthesis of Tin Enolates. Isolation of Three BINAP−Silver Complexes and Their Role in Regio- and Enantioselectivity", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 126, no. 17, 1 May 2004 (2004-05-01), pages 5360 - 5361, XP093139955, ISSN: 0002-7863, DOI: 10.1021/ja039103i
N. MOMIYAMA ET AL.: "o-nitroso aldol synthesis:catalytic enantioselective route to alfa-aminooxy carbonyl compounds via enamine intermediate", PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES, NATIONAL ACADEMY OF SCIENCES, vol. 101, no. 15, 13 April 2004 (2004-04-13), pages 5374 - 5378, XP002449131, ISSN: 0027-8424, DOI: 10.1073/pnas.0307785101
SHIM JAE HO; KIM MIN-JOON; LEE JI YEON; KIM KYOUNG HOON; HA DEOK-CHAN: "Organocatalytic asymmetric aldol reaction using protonated chiral 1,2-diamines", TETRAHEDRON LETTERS, ELSEVIER, AMSTERDAM , NL, vol. 61, no. 36, 27 July 2020 (2020-07-27), Amsterdam , NL , XP086250432, ISSN: 0040-4039, DOI: 10.1016/j.tetlet.2020.152295
SHIM JAE HO, LEE JI YEON, KIM HYEON SOO, HA DEOK-CHAN: "Protonated Chiral 1,2-Diamine Organocatalysts for N-Selective Nitroso Aldol Reaction", CATALYSTS, M D P I AG, CH, vol. 12, no. 4, CH , pages 435, XP093139958, ISSN: 2073-4344, DOI: 10.3390/catal12040435
MOMIYAMA NORIE, YAMAMOTO HISASHI: "Enantioselective O - and N -Nitroso Aldol Synthesis of Tin Enolates. Isolation of Three BINAP−Silver Complexes and Their Role in Regio- and Enantioselectivity", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, vol. 126, no. 17, 1 May 2004 (2004-05-01), pages 5360 - 5361, XP093139955, ISSN: 0002-7863, DOI: 10.1021/ja039103i
N. MOMIYAMA ET AL.: "o-nitroso aldol synthesis:catalytic enantioselective route to alfa-aminooxy carbonyl compounds via enamine intermediate", PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES, NATIONAL ACADEMY OF SCIENCES, vol. 101, no. 15, 13 April 2004 (2004-04-13), pages 5374 - 5378, XP002449131, ISSN: 0027-8424, DOI: 10.1073/pnas.0307785101
SHIM JAE HO; KIM MIN-JOON; LEE JI YEON; KIM KYOUNG HOON; HA DEOK-CHAN: "Organocatalytic asymmetric aldol reaction using protonated chiral 1,2-diamines", TETRAHEDRON LETTERS, ELSEVIER, AMSTERDAM , NL, vol. 61, no. 36, 27 July 2020 (2020-07-27), Amsterdam , NL , XP086250432, ISSN: 0040-4039, DOI: 10.1016/j.tetlet.2020.152295
SHIM JAE HO, LEE JI YEON, KIM HYEON SOO, HA DEOK-CHAN: "Protonated Chiral 1,2-Diamine Organocatalysts for N-Selective Nitroso Aldol Reaction", CATALYSTS, M D P I AG, CH, vol. 12, no. 4, CH , pages 435, XP093139958, ISSN: 2073-4344, DOI: 10.3390/catal12040435
Attorney, Agent or Firm:
MUHANN PATENT & LAW FIRM (KR)
Download PDF: