Regioselective ortho‐Palladation of [2.2]Paracyclophane Scaffolds: Accessing Planar and Central Chiral N, C‐Palladacycles. Issue 36 (27th September 2021)

• Record Type: Journal Article
• Authors: Zippel, Christoph; Bartholomeyzik, Teresa; Friedmann, Christian; Nieger, Martin; Hassan, Zahid; Bräse, Stefan
• Is Part Of: European journal of organic chemistry. Issue 36(2021)
• Page Start: 5090
• Page End: 5093
• Publication Date: 2021-09-27
• Subjects: Cyclometallation -- Palladacycles -- Planar chirality -- [2.2]Paracyclophane -- Regioselectivity; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202101066
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: In this report, we describe a series of cyclophanyl‐derived mono‐ and binuclear N, C‐palladacycles by regioselective ortho ‐palladation of amine‐functionalized [2.2]paracyclophanes. Employing Pd(OAc)2 followed by LiCl and with the subsequent modular treatment of Ph3 P, Cy3 P, and (Ph2 PCH2 )2, this strategy allows to prepare stable cyclophanyl‐derived planar and central chiral N, C‐palladacycles in a highly selective manner. The regioselective ortho ‐palladation mono‐ and bimetallic product formation was analyzed by detailed spectroscopic techniques, mass spectrometry and unambiguously confirmed by single‐crystal X‐ray analysis. Abstract : A selective palladation: Planar and central chiral cyclophanyl‐derived mono‐ and binuclear N, C‐palladacycles are prepared by regioselective ortho ‐palladation of amine‐ and imine‐functionalized [2.2]paracyclophanes employing stepwise Pd(OAc)2 and LiCl followed by modular treatment with PPh3, PCy3 and (Ph2 PCH2 )2 . The regioselective ortho ‐palladation mono‐ and bimetallic product formation was analyzed by detailed spectroscopic techniques, mass spectrometry and unambiguously confirmed by single‐crystal X‐ray analysis.