Preparation of visible-light-activated metal complexes and their use in photoredox/nickel dual catalysis.
Visible-light-activated photoredox catalysts provide synthetic chemists with the unprecedented capability to harness reactive radicals through discrete, single-electron transfer (SET) events. This protocol describes the synthesis of two transition metal complexes, [Ir{dF(CF3)2ppy}2(bpy)]PF6(1a) and [Ru(bpy)3](PF6)2(2a), that are activated by visible light. These photoredox catalysts are SET agents that can be used to facilitate transformations ranging from proton-coupled electron-transfer-mediated cyclizations to C-C bond constructions, dehalogenations, and H-atom abstractions. These photocatalysts have been used in the synthesis of medicinally relevant compounds for drug discovery, as well as the degradation of biological polymers to access fine chemicals. These catalysts are prepared from IrCl3and RuCl3, respectively, in three chemical steps. These steps can be described as a series of two ligand modifications followed by an anion metathesis. Using the cost-effective, scalable procedures described here, the ruthenium-based photocatalyst 2a can be synthesized in a 78% overall yield (∼8.1 g), and the iridium-based photocatalyst 1a can be prepared in a 56% overall yield (∼4.4 g). The total time necessary for the complete protocols ranges from ∼2 d for 2a to 5-7 d for 1a. Procedures for applying each catalyst in representative photoredox/Ni cross-coupling to form Csp3-Csp2 bonds using the appropriate radical precursor-organotrifluoroborates with 1a and bis(catecholato)alkylsilicates with 2a-are described. In addition, more traditional photoredox-mediated transformations are included as diagnostic tests for catalytic activity.
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, USA.
Christopher B
0000-0002-5530-8606
CB
Kelly
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, USA.
Niki R
NR
Patel
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, USA.
David N
DN
Primer
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, USA.
Matthieu
M
Jouffroy
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, USA.
John C
JC
Tellis
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, USA.
Gary A
GA
Molander
D002384:Catalysis; D060326:Chemistry Techniques, Synthetic / Q000379:methods*; D008027:Light; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D055668:Photochemical Processes
D009942:Organometallic Compounds; D009532:Nickel