Expanding the Boxmi Ligand family

• Verfasst von: Blasius, Clemens K. [VerfasserIn]
• Verfasst von: Bürgy, David [VerfasserIn]
• Verfasst von: Michalsky, Ina [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Gade, Lutz H. [VerfasserIn]
• Titel: Expanding the Boxmi Ligand family
• Titelzusatz: synthesis and application of NON and NSN ligands
• Verf.angabe: Clemens K. Blasius, Bing-Tao Ren, David Bürgy, Yan-Kai Liu, Bin Li, Ina Michalsky, Hubert Wadepohl, Qing-Hai Deng, and Lutz H. Gade
• E-Jahr: 2020
• Jahr: April 14, 2020
• Umfang: 13 S.
• Fussnoten: Gesehen am 20.07.2020
• Titel Quelle: Enthalten in: The journal of organic chemistry
• Ort Quelle: [S.l.] : American Chemical Society, 1936
• Jahr Quelle: 2020
• Band/Heft Quelle: 85(2020), 10, Seite 6719-6731
• ISSN Quelle: 1520-6904
• DOI: doi:10.1021/acs.joc.0c00751
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1725171678

Abstract

Two synthetic strategies for a new family of neutral NON ligands featuring a “bis(oxazolinylmethylidene)isobenzofuran” framework (boxman) are reported. A Pd-mediated cyclization reaction forming the isobenzofuran core constitutes the key reaction in the eight-step synthetic route to the nonbackbone-methylated target compound H,Rboxman. In contrast, the introduction of two additional methyl groups provides stereochemical control during backbone construction and thereby access to the methylated derivative Me,Rboxman, which was synthesized in five steps and improved yields. In addition, the synthetic sequence was transferred to the thio analogue, providing access to the NSN ligand H,Rboxmene. Subsequent complexation experiments with iron and cobalt chloride precursors afforded the four-coordinated chlorido complexes Me,RboxmanMCl2 (R = Ph, iPr; M = Fe, Co) and established the boxman family as trans-chelating, bidentate bis(oxazoline) ligands. Application of the latter in the nickel(II)- and zinc(II)-catalyzed α-fluorination of β-ketoesters and oxindoles (up to 98% yield and 94% ee) demonstrated their suitability for enantioselective catalysis.