title: Enantioselective Rhodium-Catalyzed Atom-Economical Macrolactonization.
abstract: A highly attractive route toward macrolactones, which form the cyclic scaffold of a multitude of diverse natural compounds, is described. Although many chemical approaches to this structural motif have been explored, an asymmetric variant of the cyclization is unprecedented. Herein we present an enantioselective macrolactonization through an intramolecular atom-economical rhodium-catalyzed coupling of ω-allenyl-substituted carboxylic acids. The use of a modified diop ligand, chiral DTBM-diop, led to high enantioselectivity (up to 93 % ee). The reaction tolerated a large variety of functionalities, including α,β-unsaturated carboxylic acids and depsipeptides, and provided the desired macrocycles with very high enantio- and diastereoselectivity.
authors.affiliation: Institut für Organische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104, Freiburg im Breisgau, Germany.
authors.forename: Stephanie
authors.initials: S
authors.lastname: Ganss
authors.affiliation: Institut für Organische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104, Freiburg im Breisgau, Germany. bernhard.breit@chemie.uni-freiburg.de.
authors.forename: Bernhard
authors.identifier: 0000-0002-2514-3898
authors.initials: B
authors.lastname: Breit
keywords: asymmetric catalysis; hydrooxycarbonylation; ligand design; macrolactonization; rhodium