Chiral Cp-Rhodium(III)-Catalyzed Asymmetric Hydroarylations of 1,1-Disubstituted Alkenes

• Published in: Angewandte Chemie International Edition Vol. 53; no. 2; pp. 507 - 511
• Main Authors: Ye, Baihua, Donets, Pavel A., Cramer, Nicolai
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 07-01-2014; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkenes; asymmetric catalysis; Asymmetry; Backbone; Bonding; cyclopentadienyl ligands; CH activation; hydroarylation; Ligands; rhodium; Strategy; Transformations; cyclopentadienyl ligands; CH activation; asymmetric catalysis; hydroarylation; rhodium
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201309207

Metal‐catalyzed functionalizations at the ortho position of a directing group have become an efficient bond‐forming strategy. A wide range of transformations that employ Cp*RhIII catalysts have been described, but despite their synthetic potential, enantioselective variants that use chiral versions of the Cp* ligand remain scarce (Cp*=pentamethyl cyclopentadienyl). Cyclopentadienyl compounds with an atropchiral biaryl backbone are shown to be suitable ligands for the efficient intramolecular enantioselective hydroarylation of aryl hydroxamates. Dihydrofurans that bear methyl‐substituted quaternary stereocenters are thus obtained by CH functionalization under mild conditions.
Dihydrofurans that bear methyl‐substituted quaternary stereocenters were obtained by rhodium(III)‐catalyzed enantioselective hydroarylation and CH functionalization at mild conditions. The use of chiral cyclopentadienyl ligands with a biaryl backbone led to excellent enantioselectivities.