Enantioselective Rhodium-Catalyzed Synthesis of Branched Allylic Amines by Intermolecular Hydroamination of Terminal Allenes†
Dr. Michael L. Cooke
Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
Search for more papers by this authorKun Xu
Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Bernhard Breit
Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)Search for more papers by this authorDr. Michael L. Cooke
Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
Search for more papers by this authorKun Xu
Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Bernhard Breit
Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)
Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg im Breisgau (Germany)Search for more papers by this authorThis work was supported by the DFG, the International Research Training Group “Catalysts and Catalytic Reactions for Organic Synthesis” (IRTG 1038), the Fonds der Chemischen Industrie, and the Krupp Foundation. We thank Umicore, BASF, and Wacker for generous gifts of chemicals.
Graphical Abstract
Branching out: The rhodium-catalyzed enantioselective hydroamination of monosubstituted allenes with anilines permits the atom-economic synthesis of valuable branched allylic amines. In contrast to previous linear selective allene hydroaminations, a RhI/Josiphos catalyst system (see scheme; cod=1,5-cyclooctadiene, DCE=1,2-dichloroethane) allows branched allylic amines to be obtained with perfect regioselectivity, high yield, and good enantioselectivity.
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