title: Exploiting the Multidentate Nature of Chiral Disulfonimides in a Multicomponent Reaction for the Asymmetric Synthesis of Pyrrolo[1,2-a]indoles: A Remarkable Case of Enantioinversion.
abstract: A new multicomponent coupling reaction for the enantioselective synthesis of pyrrolo[1,2-a]indoles under the catalysis of a chiral disulfonimide is described. The high specificity of the reaction is a consequence of the multidentate character of the Brønsted acid catalyst. Insights from DFT calculations helped explain the unexpected high enantioselectivity observed with the simplest 3,3'-unsubstituted binaphthyl catalyst as a result of transition-state stabilization by a network of cooperative noncovalent interactions. The remarkable enantioinversion resulting from the simple introduction of substituents at 3- and 3'-positions, the first reported example of this phenomenon in the context of binaphthalene-derived Brønsted acid catalysis, was instead attributed to destabilizing steric interactions.
authors.affiliation: Instituto Universitario de Química Organometálica "Enrique Moles", Universidad de Oviedo, Julián Clavería, 8, 33006, Oviedo, Spain.
authors.forename: Alicia
authors.initials: A
authors.lastname: Galván
authors.affiliation: Departamento de Química Orgánica (CINBIO and IBI), Universidade de Vigo, As Lagoas-Marcosende, 36310, Vigo, Spain.
authors.forename: Adán B
authors.initials: AB
authors.lastname: González-Pérez
authors.affiliation: Departamento de Química Orgánica (CINBIO and IBI), Universidade de Vigo, As Lagoas-Marcosende, 36310, Vigo, Spain.
authors.forename: Rosana
authors.initials: R
authors.lastname: Álvarez
authors.affiliation: Departamento de Química Orgánica (CINBIO and IBI), Universidade de Vigo, As Lagoas-Marcosende, 36310, Vigo, Spain.
authors.forename: Angel R
authors.initials: AR
authors.lastname: de Lera
authors.affiliation: Instituto Universitario de Química Organometálica "Enrique Moles", Universidad de Oviedo, Julián Clavería, 8, 33006, Oviedo, Spain. fjfv@uniovi.es.
authors.forename: Francisco J
authors.initials: FJ
authors.lastname: Fañanás
authors.affiliation: Instituto Universitario de Química Organometálica "Enrique Moles", Universidad de Oviedo, Julián Clavería, 8, 33006, Oviedo, Spain. frodriguez@uniovi.es.
authors.forename: Félix
authors.initials: F
authors.lastname: Rodríguez
keywords: acid catalysis; heterocycles; homogeneous catalysis; organocatalysis; synthetic methods