A Hemilabile NHC‐Gold Complex and its Application to the Redox Neutral 1,2‐Oxyarylation of Feedstock Alkenes

Abstract

We describe a AuI complex of a hemi‐labile (C^N) N‐heterocyclic carbene ligand that is able to mediate oxidative addition of aryl iodides. Detailed computational and experimental investigations have been undertaken to verify and rationalize the oxidative addition process. Application of this initiation mode has resulted in the first examples of “exogenous oxidant‐free” AuI/AuIII catalyzed 1,2‐oxyarylations of ethylene and propylene. These demanding yet powerful processes establish these commodity chemicals as nucleophilic‐electrophilic building blocks in catalytic reaction design.

Gold(I) N‐heterocyclic carbene (NHC) complexes containing 6‐mercaptopurine derivatives and their in vitro anticancer and anti‐inflammatory effects

“…Cl] = 0.02; 124.36 q, 3.8, (C13, II), Δδ 2-L2 = À0.15; 124.32 q, 3.8, (C13, I), Δδ 19,31, (I) , Δδ 3-[Au(iPr)Cl] = 0.02; 7.57, 2H, t, 7.8, HC 19,31,(II) , Δδ 3-[Au(iPr)Cl] = À0.05; 7.49, 2H, d, 8.0, HC 11,15,(II) , Δδ 3-L3 = À0.10; 7.46, 2H, d, 8.0, HC 11,15, (I) , Δδ 3-L3 = À0.13; 7.45, 1H, s, HC 8, (II) , Δδ 3-L3 = À1.10; 7.45, 4H, t, 7.8, HC 18,20;30,32, (I) , Δδ 3-[Au(ipr)Cl] = À0.01; 7.44, 4H, t, 7.8, HC 18,20;30,32,(II) , Δδ 3-[Au(ipr)Cl] = À0.02; 7.35, 1H, s, HC 8, (I) , Δδ 3-L3 = À1.20; 7.16, 2H, d, 8.0, HC 12,14, (I) , Δδ 3-L3 = 0.01; 7.09, 2H, d, 8.0, HC 12,14,(II) , Δδ 3-L3 = À0.06; 4.61, 2H, s, HC 9, (II) , Δδ 3-L3 = À0.11; 4.44, 2H, s, HC 9, (I) , Δδ 3-L3 = À0.28; 2.69, 4H, sep, 6.8, HC 22,25,34,37,(II) , Δδ 3-[Au(iPr)Cl] = 0.06; 2.67, 4H, sep, 6.8, HC 22,25,34,37, (I) , Δδ 3-[Au(iPr)Cl] = 0.04; 1.44, 24H, d, 6.8, HC 23,24,26,27,35,36,38,39,(IIa) , Δδ 3-[Au(iPr)Cl] = 0.08; 1.32, 24H, d, 6.8, HC 23,24,26,27,35,36,38,39,(Ia) , Δδ 3-[Au (iPr) Cl] = À0.04; 1.28, 24H, d, 6.8, HC 23,24,…”

“…13 C-NMR, d 7 -DMF, T = 25 C, relative to TMS, δ Cl] = 0.13; 8.19, 2H, s, HC 3,7, (II) , Δδ 4-[Au(iPr)Cl] = 0.11; 7.74, 2H, d, 8.0, HC 11,15, (I) , Δδ 4-L4 = À0.04; 7.72, 2H, d, 8.0, HC 11,15,(II) , Δδ 4-L4 = À0.16; 7.68, 2H, d, 8.0, HC 12,14,(II) , Δδ 4-L4 = 0.01; 7.67, 2H, d, 8.0, HC 12,14, (I) , Δδ 4-L4 = 0.00; 7.64, 2H, t, 7.8, HC 19,31, (I) , Δδ 4-[Au(iPr) Cl] = 0.02; 7.56, 2H, t, 7.8, HC 19,31,(II) , Δδ 4-[Au(iPr) Cl] = À0.06; 7.46, 4H, t, 7.8, HC 18,20;30,32, (I) , Δδ 4-[Au(iPr) Cl] = 0.00; 7.45, 4H, t, 7.8, HC 18,20;30,32,(II) , Δδ 4-[Au(iPr) Cl] = À0.01; 7.45, 1H, s, HC 8, (II) , Δδ 4-L4 = À1.12; 7.35, 1H, s, HC 8, (I) , Δδ 4-L4 = À1.22; 4.71, 2H, s, HC 9, (II) , Δδ 4-L4 = À0.10; 4.53, 2H, s, HC 9, (I) , Δδ 4-L4 = À0.28; 2.69, 4H, sep, 6.8, HC 22,25,34,37,(II) , Δδ 4-[Au(iPr)Cl] = 0.06; 2.68, 4H, sep, 6.8, HC 22,25,34,37, (I) , Δδ 4-[Au(iPr)Cl] = 0.05; 1.43, 24H, d, 6.8, HC 23,24,26,27,35,36,38,39,(IIa) , Δδ 4-[Au(iPr)Cl] = 0.07; 1.32, 24H, d, 6.8, HC 23,24,26,27,35,36,38,39,(Ia) , Δδ 4-[Au (iPr) Cl] = À0.04; 1.27, 24H, d, 6.8, HC 23,…”

“…HC 23,24,26,27,35,36,38,39,(Ib) , Δδ HL 4 (R = p-CF 3 ), 1 H-NMR, d 7 -DMF, T = 25 C, relative to TMS, δ (ppm), J (Hz): 13.70, 1H, br, HN 9 ; 8.76, 1H, s, HC 2 ; 8.57, 1H, s, HC 8 ; 7.78, 2H, d, 8.2, HC 10, 14 ; 7.67, 1H, d, 8.2, HC 11,13 ; 4.81, 2H, bs, HC 9 . Cl] = 0.15; 8.19, 2H, s, HC 3,7, (II) , Δδ 5-[Au(iPr)Cl] = 0.11; 8.02, 1H, d, 8.2, HC 12, (I) , Δδ 5-L5 = À0.03; 7.99, 1H, d, 8.2, HC 12, (II) , Δδ 5-L5 = À0.06;; 7.85, 1H, d, 7.9, HC 15, (I) , Δδ 5-L5 = À0.08; 7.72, 1H, t, 8.0, HC 14, (II) , Δδ 5-L5 = 0.04; 7.71, 1H, d, 7.9, HC 15, (II) , Δδ 5-L5 = À0.22; 7.71, 1H, t, 8.0, HC 14, (I) , Δδ 5-L5 = 0.03; 7.63, 1H, t, 8.0, HC 13, (I) , Δδ 5-L5 = 0.10; 7.60, 2H, t, 7.8, HC 19,31, (I) , Δδ 5-[Au(iPr) Cl] = À0.02; 7.56, 2H, t, 7.8, HC 19,31,(II) , Δδ 5-[Au(iPr) Cl] = À0.06; 7.55, 1H, t, 8.0, HC 13, (II) , Δδ 5-L5 = 0.02; 7.47, 4H, t, 7.8, HC 18,20;30,32, (I) , Δδ 5-[Au(iPr)Cl] = 0.01; 7.44, 4H, t, 7.8, HC 18,20;30,32,(II) , Δδ 5-[Au(iPr)Cl] = À0.02; 7.43, 1H, s, HC 8, (II) , Δδ 5-L5 = À1.14; 7.37, 1H, s, HC 8, (I) , Δδ 5-L5 = À1.20; 4.91, 2H, s, HC 9, (II) , Δδ 5-L5 = À0.11; 4.71, 2H, s, HC 9, (I) , Δδ 5-L5 = À0.31; 2.70, 4H, sep, 6.8, HC 22,25,34,37, (I) , Δδ 5-[Au(iPr)Cl] = 0.07; 2.70, 4H, sep, 6.8, HC 22,25,34,37,(II) , Δδ 5-[Au(iPr)Cl] = 0.07; 1.43, 24H, d, 6.8, HC 23,24,26,27,35,36,38,39,(IIa) , Δδ 5-[Au(iPr)Cl] = 0.07; 1.36, 24H, d, 6.8, HC 23,…”

“…One of the groups of such complexes can be represented by gold(I)-N-heterocyclic carbene (NHC) ones, which, apart from biological features, reveal some catalytic abilities. [9][10][11] As for the biological effects of Au(I)-NHC complexes, specifically those of anticancer, many papers have been published up to now, and some reviews on this topic can be found in the references. [12][13][14][15] Some concrete results regarding this type of compounds and their antiproliferative effects can be found in the literature.…”

DFT-Enabled Development of Hemilabile (P∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

“…Very recently, interest has been focused toward the development of catalysts bearing (C ∧ N) ligands. The same authors, and Zhang and Szostak, independently reported that the ImPy carbene-based ligand 11 represented a promising alternative to the use of MeDalPhos . The related (MIC ∧ N)­AuCl complex 10 developed by the group of Ribas appeared to be less reactive .…”