Water Phase, Room Temperature, Ligand‐Free Suzuki–Miyaura Cross‐Coupling: A Green Gateway to Aryl Ketones by C–N Bond Cleavage

Abstract

We report herein a green strategy for synthesis of aryl ketones from twisted amides by using Pd(OAc)2 as catalysts. This method shows high functional group tolerance to offer a variety of ketones in good yields under mild conditions (up to 94 %). Notably, this methodology demonstrates the first water phase, room temperature, ligand‐free Suzuki–Miyaura coupling through C–N bond cleavage, which is environmentally friendly and might facilitate the development of amide based green chemistry.

Acylboronates in Polarity-Reversed Generation of Acyl Palladium(II) Intermediates

“…(4-Methoxyphenyl)(phenyl)methanone (3a) [3] Yellow solid; 0.1 mmol scale: 66% yield, 0.066 mmol, 14.0 mg; 1 mmol scale: 64% yield, 0.643 mmol, 136. (3-Methoxyphenyl)(phenyl)methanone (3b) [3] Yellow oil; 61% yield, 0.061 mmol, 12.9 mg; 1 H NMR (500 MHz, CDCl3) (2-Methoxyphenyl)(phenyl)methanone (3c) [3] Yellow oil; 59% yield, 0.059 mmol, 12.…”

“…Mesityl(phenyl)methanone (3i) [6] Yellow oil; 26 % yield, 0.026 mmol, 5. Benzophenone (3j) [3] Off-white solid; 56% yield, 0.056 mmol, 10. Naphthalen-2-yl(phenyl)methanone (3k) [3] Yellow oil; 43% yield, 0.043 mmol, 10.0 mg; 1 H NMR (500 MHz, CDCl3) (4-Chlorophenyl)(phenyl)methanone (3l) [3] White solid; 38% yield, 0.038 mmol, 8.…”

“…Benzophenone (3j) [3] Off-white solid; 56% yield, 0.056 mmol, 10. Naphthalen-2-yl(phenyl)methanone (3k) [3] Yellow oil; 43% yield, 0.043 mmol, 10.0 mg; 1 H NMR (500 MHz, CDCl3) (4-Chlorophenyl)(phenyl)methanone (3l) [3] White solid; 38% yield, 0.038 mmol, 8. (6-Methoxypyridin-3-yl)(phenyl)methanone (3p) [7] Colorless oil; 30% yield, 0.030 mmol, 6.…”

“…(4-Methoxyphenyl)(phenyl)methanone (3a) [3] Yellow solid; 0.1 mmol scale: 66% yield, 0.066 mmol, 14.0 mg; 1 mmol scale: 64% yield, 0.643 mmol, 136.5 mg; (3-Methoxyphenyl)(phenyl)methanone (3b) [3] Yellow oil; 61% yield, 0.061 mmol, 12.9 mg; (2-Methoxyphenyl)(phenyl)methanone (3c) [3] Yellow oil; 59% yield, 0.059 mmol, 12.5 mg; (4-(Dimethylamino)phenyl)(phenyl)methanone (3d) [4] Green solid; 57% yield, 0.057 mmol, 12.8 mg; (3,4-Dimethoxyphenyl)(phenyl)methanone (3e) [3] White solid; 51% yield, 0.051 mmol, 12.3 mg; Phenyl(p-tolyl)methanone (3f) [3] Yellow oil; 41% yield, 0.041 mmol, 8 mg; Phenyl(o-tolyl)methanone (3g) [3] Colorless oil; 54% yield, 0.054 mmol, 10.6 mg; (2,6-Dimethylphenyl)(phenyl)methanone (3h) [5] Yellow solid; 68% yield, 0.068 mmol, 14.2 mg;…”

“…2 Acylboron compounds, which are a class of functionalized carbonyl group-containing molecules, have emerged as useful reagents in organic synthesis. 3,4 While effective as boroncontaining building blocks, these molecules are not stable in their free boronic acid form. 5 Synthetic applications of acylboronates are enabled by the utilization of a MIDA (Nmethyliminodiacetic acid) ligand 4c-g, 7 or potassium organotrifluoroborates, 4a,b,g,h which provide enhanced stability to borylated compounds.…”