Palladium catalyzed addition of arylboronic acid or indole to nitriles: synthesis of aryl ketones

Binding Mode and Structure–Activity Relationships of ITE as an Aryl Hydrocarbon Receptor (AhR) Agonist

“…General procedure for the synthesis of compounds 11 – 16 : Pd(OAc) 2 (5 mol %), bipyridine (5 mol %), and the corresponding nitrile derivative (1.2 mmol) were sequentially added to a mixture of indole 19 (1 mmol) in dioxane/AcOH/H 2 O (50:20:30, v / v / v , 2 mL mmol −1 ), and the resulting mixture was stirred at 100 °C for 24 h. The reaction mixture was neutralized by adding a saturated aqueous solution of NaHCO 3 (20 mL) and extracted with EtOAc (3×15 mL). The combined organic extracts were washed with H 2 O (20 mL) and brine (20 mL), dried over anhydrous Na 2 SO 4 , and concentrated under reduced pressure.…”

“…(1 H ‐Indol‐3‐yl)(phenyl)methanone (11) : The title compound was isolated (49 mg, 0.22 mmol, 22 % yield) as a brown solid: mp: 168–172 °C; 1 H NMR ([D 6 ]DMSO, 400 MHz): δ =12.09 (brs, 1 H), 8.25–8.27 (d, J= 6.84 Hz, 1 H), 7.94 (s, 1 H), 7.79 (d, J= 7.5 Hz, 2 H), 7.52–7.62 (m, 4 H), 7.22–7.28 ppm (m, 2 H); 13 C NMR ([D 6 ]DMSO, 100.6 MHz): δ =190.4, 141.0, 137.2, 136.3, 131.5, 128.8 (2×), 126.7, 123.6, 122.4, 121.9, 115.4, 112.7 ppm; HPLC t R : 7.0 min, eluent: H 2 O/CH 3 CN (1:1, v / v ).…”

“…The combined organic extracts were dried over anhydrous Na (10): [29] Diethylaminosulfurtrifluoride (DAST,1 .5 mmol, 0.2 mL) was added to as uspension of 18 (0.7 mmol, 0.2 g) in freshly distilled CH 2 Cl 2 (5 mL) at À78 8Cu nder argon atmosphere. The resulting mixture was allowed to warm to room temperature and stirred for 6h.R eaction progress was monitored by TLC (eluent: General procedure for the synthesis of compounds 11-16: [31] Pd(OAc) 2 (1H-Indol-3-yl)(phenyl)methanone (11): [31] (1H-Indol-3-yl)(thiophen-2-yl)methanone (12): [32] Furan-2-yl(1H-indol-3-yl)methanone (14): [33] (1H-Indol-3-yl)(pyridin-2-yl)methanone (15): [33] The title compound was isolated (…”

Transition Metal‐Catalyzed CH Activation of Indoles

“…Reaction Couplingpartner/reagentC atalyst References 1a rylation aryl halides Pd [101,102,104,105] 2b enzoic acids Pd [107] 3a rylhydrazines Pd [108] 4c yclohexanones Pd [109] 5d iaryliodonium salts Cu [110] 6N -heterocyclic compounds Pd [111][112][113][114] 7a lkynylation alkynes Au [115] 8b enzylation benzylic alcohols Au [116] 9o lefination alkenes Pd [117,118] 10 acylation benzaldehydes Pd [119] 11 TMEDA Cu [120] 12 nitrilesP d [121] 13 CO and alcohols Rh [122] 14 a-amino carbonyl compounds Cu [123] 15 Pd [124] 16 synthesis of bisindoles alcohols Pd [141,142] 17 aldehydes Ag [143] 18 amines Pd [144] 19 annulation alkenes Pd 21 cyanation CuCN Pd [150] 22 K 4 [Fe(CN) 6 ]P d [151] 23 t-BuNC Pd [152] 24 NH 4 HCO 3 and DMSOP d [153] 25 amidation isocyanides Pd [154] Scheme 44. Pd-catalyzedarylation.…”

“…3-Acylindoles were also accessible from indolesa nd nitriles [121] in mostly good yields (Scheme 58).…”