Title:
REGIOSELECTIVE OXIDATION OF HETEROCYCLIC ALPHA-AMINO AMIDES
Document Type and Number:
WIPO Patent Application WO/2021/214278
Kind Code:
A3
Abstract:
The present invention relates to regioselective chemical and electrochemical processes for the preparation of an oxidized heterocyclic alpha-amino amide compounds. By applying specific catalysts or catalyst systems during chemical oxidation or by applying particular electrochemical oxidation conditions the present invention provides access to valuable alpha amino amide compounds, which are oxidized at the heterocyclic amino group by regioselective introduction of either a hydroxyl or a keto group. In a more particular embodiment, the present invention describes a chemical oxidation reaction, which advantageously is applicable in the enantioselective synthesis of valuable oxidized heterocyclic alpha-amino amide compounds, like levetiracetam, brivaracetam or the synthesis of piracetam. Another aspect of the present invention relates to a process for the electrochemical recycling of alkali perhalogenate oxidants as spent during said regioselective oxidation reactions of the invention. Still another aspect of the invention relates to the electrochemical preparation of perhalogenates.
Inventors:
WALDVOGEL SIEGFRIED R (DE)
ARNDT SEBASTIAN (DE)
WEIS DOMINIK (DE)
DONSBACH KAI (DE)
NAUTH ALEXANDER MATTHIAS (DE)
OPATZ TILL (DE)
ARNDT SEBASTIAN (DE)
WEIS DOMINIK (DE)
DONSBACH KAI (DE)
NAUTH ALEXANDER MATTHIAS (DE)
OPATZ TILL (DE)
Application Number:
PCT/EP2021/060639
Publication Date:
December 02, 2021
Filing Date:
April 23, 2021
Export Citation:
Assignee:
PHARMAZELL GMBH (DE)
International Classes:
C07D207/27; B01J23/46; C12N9/88; C12P13/02; C12P17/10; C12P41/00; C25B1/24; C25B3/07; C25B3/09; C25B9/15; C25B9/19; C25B11/043
Domestic Patent References:
| WO2008077035A2 | 2008-06-26 | |||
| WO2006095362A1 | 2006-09-14 | |||
| WO2004055243A1 | 2004-07-01 | |||
| WO2018002548A1 | 2018-01-04 |
Other References:
GRIFFITHS ROBERT J. ET AL: "Transition-Metal-Free Amine Oxidation: A Chemoselective Strategy for the Late-Stage Formation of Lactams", vol. 19, no. 4, 8 February 2017 (2017-02-08), US, pages 870 - 873, XP055780586, ISSN: 1523-7060, Retrieved from the Internet [retrieved on 20170208], DOI: 10.1021/acs.orglett.7b00021
RAFIEE MOHAMMAD ET AL: "Electrochemical Oxidation of Alcohols and Aldehydes to Carboxylic Acids Catalyzed by 4-Acetamido-TEMPO: An Alternative to "Anelli" and "Pinnick" Oxidations", vol. 8, no. 7, 11 June 2018 (2018-06-11), US, pages 6738 - 6744, XP055780868, ISSN: 2155-5435, Retrieved from the Internet [retrieved on 20180611], DOI: 10.1021/acscatal.8b01640
SANCHEZ-CARRETERO A ET AL: "Electrochemical production of perchlorates using conductive diamond electrolyses", CHEMICAL ENGENEERING JOURNAL, ELSEVIER, AMSTERDAM, NL, vol. 166, no. 2, 15 January 2011 (2011-01-15), pages 710 - 714, XP027575940, ISSN: 1385-8947, [retrieved on 20101224]
JANSSEN L J J: "Periodate preparation by electrolytic oxidation of iodate, comprises use of lithium iodate as electrolyte and electrode comprising lead, lead alloy or electrically conducting diamond", WPI / 2017 CLARIVATE ANALYTICS,, vol. 2001, no. 49, 23 April 2001 (2001-04-23), XP002802952
ORCHIDEH AZIZI ET AL: "Mechanism of Perchlorate Formation on Boron-Doped Diamond Film Anodes", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 45, no. 24, 15 December 2011 (2011-12-15), US, pages 10582 - 10590, XP055347538, ISSN: 0013-936X, DOI: 10.1021/es202534w
RAFIEE MOHAMMAD ET AL: "Electrochemical Oxidation of Alcohols and Aldehydes to Carboxylic Acids Catalyzed by 4-Acetamido-TEMPO: An Alternative to "Anelli" and "Pinnick" Oxidations", vol. 8, no. 7, 11 June 2018 (2018-06-11), US, pages 6738 - 6744, XP055780868, ISSN: 2155-5435, Retrieved from the Internet
SANCHEZ-CARRETERO A ET AL: "Electrochemical production of perchlorates using conductive diamond electrolyses", CHEMICAL ENGENEERING JOURNAL, ELSEVIER, AMSTERDAM, NL, vol. 166, no. 2, 15 January 2011 (2011-01-15), pages 710 - 714, XP027575940, ISSN: 1385-8947, [retrieved on 20101224]
JANSSEN L J J: "Periodate preparation by electrolytic oxidation of iodate, comprises use of lithium iodate as electrolyte and electrode comprising lead, lead alloy or electrically conducting diamond", WPI / 2017 CLARIVATE ANALYTICS,, vol. 2001, no. 49, 23 April 2001 (2001-04-23), XP002802952
ORCHIDEH AZIZI ET AL: "Mechanism of Perchlorate Formation on Boron-Doped Diamond Film Anodes", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 45, no. 24, 15 December 2011 (2011-12-15), US, pages 10582 - 10590, XP055347538, ISSN: 0013-936X, DOI: 10.1021/es202534w
Attorney, Agent or Firm:
REITSTÖTTER KINZEBACH (DE)
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