Single‐Face/All‐cis Arene Hydrogenation by a Supported Single‐Site d0 Organozirconium Catalyst. Issue 17 (17th March 2016)

• Record Type: Journal Article
• Authors: Stalzer, Madelyn Marie; Nicholas, Christopher P.; Bhattacharyya, Alak; Motta, Alessandro; Delferro, Massimiliano; Marks, Tobin J.
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 17(2016)
• Page Start: 5263
• Page End: 5267
• Publication Date: 2016-03-17
• Subjects: DFT calculations -- organozirconium catalyst -- stereoselective hydrogenation -- sulfated oxides -- supported catalysts; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201600345
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The single‐site supported organozirconium catalyst Cp*ZrBz2 /ZrS (Cp*=Me5 C5, Bz=benzyl, ZrS=sulfated zirconia) catalyzes the single‐face/all‐cis hydrogenation of a large series of alkylated and fused arene derivatives to the corresponding all‐cis‐cyclohexanes. Kinetic/mechanistic and DFT analysis argue that stereoselection involves rapid, sequential H2 delivery to a single catalyst‐bound arene face, versus any competing intramolecular arene π‐face interchange. Abstract : Stereocontrol is on : A single‐site supported organozirconium catalyst exhibits unprecedented all ‐cis stereo/face‐selective hydrogenation of substituted alkylarenes under mild reaction conditions. The resulting stereopure cycloalkanes offer new building blocks for value‐added fine chemicals.