Organocatalytic Asymmetric Addition of Naphthols and Electron-Rich Phenols to Isatin-Derived Ketimines: Highly Enantioselective Construction of Tetrasubstituted Stereocenters†
Marc Montesinos-Magraner
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorDr. Carlos Vila
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorRubén Cantón
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorProf. Dr. Gonzalo Blay
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorDr. Isabel Fernández
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorProf. Dr. M. Carmen Muñoz
Departament de Física Aplicada, Universitat Politècnica de València, Camino de Vera s/n, 46022 València (Spain)
Search for more papers by this authorCorresponding Author
Prof. Dr. José R. Pedro
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)Search for more papers by this authorMarc Montesinos-Magraner
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorDr. Carlos Vila
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorRubén Cantón
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorProf. Dr. Gonzalo Blay
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorDr. Isabel Fernández
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Search for more papers by this authorProf. Dr. M. Carmen Muñoz
Departament de Física Aplicada, Universitat Politècnica de València, Camino de Vera s/n, 46022 València (Spain)
Search for more papers by this authorCorresponding Author
Prof. Dr. José R. Pedro
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)
Departament de Química Orgànica, Facultat de Química, Universitat de València, Dr. Moliner 50, 46100 Burjassot, València (Spain)Search for more papers by this authorFinancial support from the MINECO (Gobierno de España; CTQ2013-47494-P) and from Generalitat Valenciana (ISIC2012/001) is gratefully acknowledged. M.M.-M. thanks the Universitat de València for a predoctoral grant. C.V. thanks MINECO for a JdC contract.
Graphical Abstract
Gentle persuasion: A quinine-derived thiourea organocatalyst was found to promote the asymmetric addition of naphthols and activated phenols to ketimines derived from isatins (see scheme; Boc=tert-butoxycarbonyl). The reaction under mild conditions afforded chiral 3-amino-2-oxindoles containing a quaternary stereocenter in high yields (up to 99 %) with excellent enantioselectivity (up to 99 % ee).
Abstract
A quinine-derived thiourea organocatalyst promoted the highly enantioselective addition of naphthols and activated phenols to ketimines derived from isatins. The reaction afforded chiral 3-amino-2-oxindoles with a quaternary stereocenter in high yields (up to 99 %) with excellent enantioselectivity (up to 99 % ee). To the best of our knowledge, this transformation is the first highly enantioselective addition of naphthols to ketimines.
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