Mechanochemical synthesis of (hetero)aryl Au(i) complexes
Growing demand for sustainable chemical syntheses casts mechanochemistry in a new light as an environmentally benign alternative to traditional solvent-based methods. Given recent interest in Au(i) complexes for catalytic, materials, and medicinal applications, we developed a mechanochemical protocol to prepare (hetero)aryl Au(i) complexes under green conditions. The procedure reported here uses C-H or C-B activation to afford the corresponding Au(i) complexes in high yields. Our approach bypasses external heating, long reaction times and the use of toxic solvents. We demonstrate that mechanochemical C-H auration can be used on highly functionalised bioactive substrates. Mechanistic aspects of the C-H auration are discussed.
Dyrager, Christine,Gates, Paul J.,Giustra, Zachary X.,Ingner, Fredric J. L.,Novosedlik, Sebastian,Orthaber, Andreas,Pilarski, Lukasz T.
supporting information
p. 5648 - 5655
(2020/09/21)
Mild and Efficient Synthesis of Diverse Organo-AuI-L Complexes in Green Solvents
An exceptionally mild and efficient method was developed for the preparation of (hetero)aryl-AuI-L complexes using ethanol or water as the reaction medium at room temperature and Ar-B(triol)K boronates as the transmetalation partner. The reaction does not need an exogeneous base or other additives, and quantitative yields can be achieved through a simple filtration as the only required purification method, which obviates considerable waste associated with alternative workup methods. A broad reaction scope was demonstrated with respect to both the L and (hetero)aryl ligands on product Au complexes. Despite the polar reaction medium, large polycyclic aromatic hydrocarbon units can be incorporated on the Au complexes in very good to excellent yields. The approach was demonstrated for the chemoselective manipulation of orthogonally protected aryl boronates to afford a new class of N-heterocyclic carbene-Au-aryl complexes. A mechanistic rationale was proposed.
Ingner, Fredric J. L.,Schmitt, Ann-Cathrin,Orthaber, Andreas,Gates, Paul J.,Pilarski, Lukasz T.
p. 2032 - 2037
(2020/03/11)
Organogold(I) complexes: Synthesis, X-ray crystal structures and aurophilicity
The synthesis of RAuPPh3 (R = aryl) from ClAuPPh3 and Grignard RM reagents (M = Li or MgX) is described. New (vinylphenyl)gold(I) and other arylgold(I) complexes were characterized by 1H, 13C, 31P, s