Gold(I) complexes with eight-membered NHC ligands

• Verfasst von: Cervantes Reyes, Alejandro [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Verfasst von: Rudolph, Matthias [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Titel: Gold(I) complexes with eight-membered NHC ligands
• Titelzusatz: synthesis, structures and catalytic activity
• Verf.angabe: Alejandro Cervantes‐Reyes, Frank Rominger, Matthias Rudolph, and A. Stephen K. Hashmi
• E-Jahr: 2020
• Jahr: April 22, 2020
• Umfang: 11 S.
• Fussnoten: Gesehen am 02.09.2020
• Titel Quelle: Enthalten in: Advanced synthesis & catalysis
• Ort Quelle: Weinheim : Wiley-VCH, 2001
• Jahr Quelle: 2020
• Band/Heft Quelle: 362(2020), 12, Seite 2523-2533
• ISSN Quelle: 1615-4169
• DOI: doi:10.1002/adsc.202000281
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: Enynes
• Sach-SW: Expanded Ring NHC Ligands
• Sach-SW: Gold
• Sach-SW: Heterocycles
• K10plus-PPN: 1728589258
• K10plus-PPN:
  Universitätsbibliothek
• Lokale URL UB: Zum Volltext

Abstract

A series of expanded-ring NHC gold complexes of the formula (NaphtDHD−Ar)Au−X (NaphtDHD=4,5-dihydro-1H-naphtho[1,8-ef][1,3]diazocin-3(2H)-ylidene; Ar: Mes=2,4,6-trimethylphenyl, Dipp=2,6-diisopropylphenyl or Xyl=2,6-dimethylphenyl; X=Cl, NCCH3, NTf2) have been synthesized, including the first gold(I) triflimidate complex (5) stabilized by an eight-membered NHC ligand. The new organogold compounds have been characterized by mass spectrometry, IR spectroscopy, and 1H and 13C NMR spectroscopy. The structural geometries of 3 b-c and 5 have been unequivocally established by crystallographic analysis revealing broad N-C-N angles (>121°) and high buried volume values (46-54%). The first catalytic studies were carried out on the cycloisomerization of 1,6-enynes, obtaining full conversions (0.5 mol% catalyst loading) and excellent endo/exo selectivity (up to 99:1), and on the gold-catalyzed phenol synthesis. Lastly, the (NaphtDHD-Dipp)Au+ NTf2− species was subjected to a kinetic experiment in the cyclization of a N-propargyl carboxamide to evaluate the efficiency of the pre-formed catalyst (5) and the in situ activated gold complex (3 b+AgNTf2).