Multigram‐Scale Kinetic Resolution of 4‐Acetyl[2.2]Paracyclophane via Ru‐Catalyzed Enantioselective Hydrogenation: Accessing [2.2]Paracyclophanes with Planar and Central Chirality

• Published in: Advanced synthesis & catalysis Vol. 363; no. 11; pp. 2861 - 2865
• Main Authors: Zippel, Christoph, Hassan, Zahid, Parsa, Ahmad Qais, Hohmann, Jens, Bräse, Stefan
• Format: Journal Article
• Language: English
• Published: 08.06.2021
• Subjects: [2.2]Paracyclophane; Asymmetric Hydrogenation; Kinetic Resolution; Planar Chirality
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.202001536

[2.2]Paracyclophane (PCP) derivatives have been promising platforms to study the element of planar chirality and through‐space electronic communications in π‐stacked molecular systems. To access enantiomerically pure derivatives thereof, a kinetic resolution of 4‐acetyl[2.2]‐PCP employing a ruthenium‐catalyzed enantioselective hydrogenation process was developed. This method can be performed on a multigram‐scale and gives access to enantiomerically pure derivatives with planar and central chirality of (Rp)‐4‐acetyl‐PCP (≥97% ee, 43%) and (Sp,S)‐PCP derivatives (≥97% ee, 46%), which are useful intermediates for the synthesis of sterically demanding PCP‐based ligand/catalyst systems and chiral synthons for engineering cyclophane‐based chiroptical materials.