C2-symmetric chiral disulfoxide ligands in rhodium-catalyzed 1,4-addition: from ligand synthesis to the enantioselection pathway |
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Authors: | Mariz Ronaldo Poater Albert Gatti Michele Drinkel Emma Bürgi Justus J Luan Xinjun Blumentritt Sascha Linden Anthony Cavallo Luigi Dorta Reto |
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Affiliation: | 1. Organisch‐chemisches Institut, Universit?t Zürich, Winterthurerstrasse 190, 8057 Zürich (Switzerland);2. Catalan Institute for Water Research (ICRA), H2O Building, Scientific and Technological Park, University of Girona, Emili Grahit 101, 17003 Girona (Spain);3. Dipartimento di Chimica, Università degli Studi di Salerno, Via Ponte don Melillo, Fisciano (SA), 84084 (Italy) |
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Abstract: | A family of chiral C(2)-symmetric disulfoxide ligands possessing biaryl atropisomeric backbones has been synthesized by using the Andersen methodology. Complete characterization includes X-ray crystallographic studies of all ligands and some of their rhodium complexes. Their synthesis, optical purity, electronic properties, and catalytic behavior in the prototypical rhodium-catalyzed 1,4-addition of phenylboronic acid to 2-cyclohexen-1-one are presented through an in depth study of this ligand class. Density functional theory calculations on the step of the catalytic cycle that determines the enantioselectivity are presented and reinforce the first hypothetical explanations for the high levels of asymmetric induction observed. |
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Keywords: | asymmetric catalysis chiral auxiliaries conjugate addition enantioselectivity sulfoxides |
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