Title:
Pd(II)-CATALYZED ENANTIOSELECTIVE BETA-METHYLENE C(sp3)-H BOND ACTIVATION
Document Type and Number:
WIPO Patent Application WO/2017/165304
Kind Code:
A3
Abstract:
Chiral acetyl-protected aminoethyl quinoline (APAQ), pyridine and imazoline ligands are disclosed that enable Pd (II)-catalyzed enantioselective arylation or heteroarylation of ubiquitous prochiral β-methylene C-H bonds of aliphatic amides offers an alternative disconnection for constructing β-chiral centers. Systematic tuning of the ligand structure reveals that a six-membered instead of a five-membered chelation of these types of ligands with the Pd(II) is important for accelerating the C(sp3)-H activation thereby achieving enantioselectivity for quinoline and pyridine ligands.
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Inventors:
YU JIN-QUAN (US)
Application Number:
PCT/US2017/023229
Publication Date:
November 09, 2017
Filing Date:
March 20, 2017
Export Citation:
Assignee:
SCRIPPS RESEARCH INST (US)
International Classes:
C07D215/04; C07D401/06; C07D491/048; C07D491/052
Other References:
CHEMICAL ABSTRACTS, 16 November 1984, Columbus, Ohio, US; abstract no. 42182-56-9, XP055445265
CHEMICAL ABSTRACTS, 5 May 2015, Columbus, Ohio, US; abstract no. 1698515-90-0, XP055445339
HE, J. ET AL.: "Ligand-controlled C(sp3)-H arylation and olefination in synthesis of unnatural chiral a-amino acids", SCIENCE, vol. 343, no. Issue 6176, 2014, pages 1216 - 1220, XP055445174
ZHANG, X. ET AL.: "Palladium-catalyzed 13-C(sp3)-H arylation of phthaloyl alanine with hindered aryl iodides:synthesis of complex 13-aryl a-amino acids", ORGANIC & BIOMOLECULAR CHEMISTRY, vol. 14, 12 January 2016 (2016-01-12), pages 5511 - 5515, XP055445172
ENGLE, K. M. ET AL.: "Developing ligands for palladium(II)-catalyzed C-H functionalization: Intimate dialogue between ligand and substrate", JOURNAL OF ORGANIC CHEMISTRY, vol. 78, no. Issue 18, 2013, pages 8927 - 8955, XP055445175
GAO, X. ET AL.: "Enantioselective palladium-catalyzed C-H functionalization of indoles using an axially chiral 2,2' -bipyridine ligand", ANGEWENDTE CHEMIE INTERNATIONAL EDITION, vol. 54, no. 41, 2015, Weinheim, pages 11956 - 11960, XP009512803, ISSN: 1433-7851, DOI: 10.1002/anie.201504483
XU, Z.-Y. ET AL.: "Superior ligand for Pd(II)-catalyzed enantioselective arylation of C(sp3)-H bonds: chiral acetyl protected aminoethyl quinoline", SCIENCE CHINA CHEMISTRY, vol. 60, no. Issue 2, 26 December 2016 (2016-12-26), pages 165 - 166, XP036144338
CHEN, G. ET AL.: "Ligand-accelerated enantioselective methylene C(sp3)-H bond activation", SCIENCE, vol. 353, no. Issue 6303, 2 September 2016 (2016-09-02), pages 1023 - 1027, XP055445184
CHEMICAL ABSTRACTS, 5 May 2015, Columbus, Ohio, US; abstract no. 1698515-90-0, XP055445339
HE, J. ET AL.: "Ligand-controlled C(sp3)-H arylation and olefination in synthesis of unnatural chiral a-amino acids", SCIENCE, vol. 343, no. Issue 6176, 2014, pages 1216 - 1220, XP055445174
ZHANG, X. ET AL.: "Palladium-catalyzed 13-C(sp3)-H arylation of phthaloyl alanine with hindered aryl iodides:synthesis of complex 13-aryl a-amino acids", ORGANIC & BIOMOLECULAR CHEMISTRY, vol. 14, 12 January 2016 (2016-01-12), pages 5511 - 5515, XP055445172
ENGLE, K. M. ET AL.: "Developing ligands for palladium(II)-catalyzed C-H functionalization: Intimate dialogue between ligand and substrate", JOURNAL OF ORGANIC CHEMISTRY, vol. 78, no. Issue 18, 2013, pages 8927 - 8955, XP055445175
GAO, X. ET AL.: "Enantioselective palladium-catalyzed C-H functionalization of indoles using an axially chiral 2,2' -bipyridine ligand", ANGEWENDTE CHEMIE INTERNATIONAL EDITION, vol. 54, no. 41, 2015, Weinheim, pages 11956 - 11960, XP009512803, ISSN: 1433-7851, DOI: 10.1002/anie.201504483
XU, Z.-Y. ET AL.: "Superior ligand for Pd(II)-catalyzed enantioselective arylation of C(sp3)-H bonds: chiral acetyl protected aminoethyl quinoline", SCIENCE CHINA CHEMISTRY, vol. 60, no. Issue 2, 26 December 2016 (2016-12-26), pages 165 - 166, XP036144338
CHEN, G. ET AL.: "Ligand-accelerated enantioselective methylene C(sp3)-H bond activation", SCIENCE, vol. 353, no. Issue 6303, 2 September 2016 (2016-09-02), pages 1023 - 1027, XP055445184
Attorney, Agent or Firm:
GAMSON, Edward, P. et al. (US)
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