title: Hydroalumination of Ketenimines and Subsequent Reactions with Heterocumulenes: Synthesis of Unsaturated Amide Derivatives and 1,3-Diimines.
abstract: The series of differently substituted ketenimines 1 was hydroluminated using di-iso-butyl aluminum hydride. For the sterically congested ketenimine 1a, preferred hydroalumination of the C═N-bond was proven by X-ray crystallography (compound 5a). In situ treatment of the hydroaluminated ketenimines 5 with various heterocumulenes like carbodiimides, isocycanates, isothiocyanates and ketenimines as electrophiles and subsequent hydrolytic workup resulted in novel enamine derived amide species in case of N-attack (sterically less hindered ketenimines) under formation of a new C-N-bond or in 1,3-diimines by C-C-bond-formation in case of bulky substituents at the ketenimine-nitrogen atom. Furthermore, domino reactions with more than 1 equiv of the electrophile or by subsequent addition of two different electrophiles are possible and lead to polyfunctional amide derivatives of the biuret type which are otherwise not easily accessible.
authors.affiliation: †Organisch Chemisches Institut der Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany.
authors.forename: Xing
authors.initials: X
authors.lastname: Jin
authors.affiliation: ‡Institut für Anorganische und Analytische Chemie der Universität Münster, Corrensstrasse 30, D-48149 Münster, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Willeke
authors.affiliation: †Organisch Chemisches Institut der Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany.
authors.forename: Ralph
authors.initials: R
authors.lastname: Lucchesi
authors.affiliation: †Organisch Chemisches Institut der Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany.
authors.forename: Constantin-Gabriel
authors.initials: CG
authors.lastname: Daniliuc
authors.affiliation: †Organisch Chemisches Institut der Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany.
authors.forename: Roland
authors.initials: R
authors.lastname: Fröhlich
authors.affiliation: †Organisch Chemisches Institut der Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany.
authors.forename: Birgit
authors.initials: B
authors.lastname: Wibbeling
authors.affiliation: ‡Institut für Anorganische und Analytische Chemie der Universität Münster, Corrensstrasse 30, D-48149 Münster, Germany.
authors.forename: Werner
authors.initials: W
authors.lastname: Uhl
authors.affiliation: †Organisch Chemisches Institut der Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany.
authors.forename: Ernst-Ulrich
authors.initials: EU
authors.lastname: Würthwein