, trifluoroacetic acid (5 ?L, 0.06 mmol) and 1,2-dibromoethane (9 ?L, 0.10 mmol) were successively added and the suspension was heated to reflux using a heat gun and then cooled down to rt, mL) Under stirring, cobalt (II) bromide (22 mg
, 18 g, d.r.=69/31, 45%) as a white solid, mL)], 5aj, pp.142-145
, Following the general procedure H, the reaction performed with bromobenzene 1a (3.2 mL, 30 mmol), methyl acrylate 2h (4 mL, 44 mmol) and 2-thiophenecarboxaldehyde 3o (1.4 mL, 15 mmol) afforded, after purification by flash chromatography, mL SiO2 96%) as a yellow oil
, Following the general procedure H, the reaction performed with bromobenzene 1a (3.2 mL, 30 mmol), ethyl acrylate 2g (4 mL, 38 mmol) and iso-butyraldehyde 3q (1.35 mL, 15 mmol) afoorded, after purification by flash chromatography, mL SiO2 89%) as a yellow oil
, 400 mL)], 5am (3.63 g, 92%) as a yellow oil
, 11 mmol) were successively added and the suspension was heated to reflux using a heat gun and then cooled down to rt Cobalt (II) bromide (22 mg, 0.1 mmol) and 1,10-phenanthroline (18 mg, 0.1 mmol) were added and the mixture was stirred for a few minutes at room temperature equiv), electrophile 3 (1.0 mmol) and ZnBr2L24 (103 mg, 0.2 mmol, 20 mol%) were successively added and the tube was sealed. The reaction was stirred at 80 °C (external temperature) for 16 h. Then, the reaction mixture was poured into sat. aq. NH4Cl (20 mL) and the resulting solution was extracted with EtOAc (3x20 mL) The combined organic layers were washed with brine, mL), trimethylsilyl chloride (10 ?L, p.2
, Following the general procedure I, the reaction performed with bromobenzene 1a (0,158 mL, 1.5 mmol), ethyl acrylate 2g (0.22 mL, 2.0 mmol) and o-tolualdehyde 3ab (0,116 mL, 1.0 mmol) afforded, after purification by flash chromatography [100 mL SiO2, 53%) as a yellow oil
, mL)], 4j (300 mg, d.r.=52/48, 64%) as a white solid, pp.118-120
, 1.89 (br s, 4H), 0.88 (t, J=7.1 Hz, 3H), 0.73 (t, J=7.1 Hz, 3H)
, 18 (d, J= 7.0 Hz, 2H), 1.71 (s, 3H), 1.57-1.50 (m, 2H), 1.49 (s, 3H), pp.3534-3535
, 10 mmol) and allyl chloride (12 ?L, 0.15 mmol) were successively added and the suspension was heated to reflux using a heat gun and then cooled down to rt Anhydrous cobalt bromide (22 mg, 0.1 mmol), 1-10 phenanthroline (18 mg, 0.1 mmol) were added and stirred for a few minutes at room temperature. Then, halogenated aromatic 1 (1.5 mmol) and electrophile 3 (1.0 mmol) were successively added, and the reaction was stirred at 80 °C (external temperature) for 16 h. Then, the reaction mixture was poured into sat. aq. NH4Cl (20 mL) and the resulting solution was extracted with EtOAc (3x20 mL) The combined organic layers were washed with brine, trifluoroacetic acid (8 ?L
, 168 mL, 1.5 mmol) or bromobenzene 1a (0.158 mL, 1.5 mmol) or chlorobenzene 1z (0.148 mL, 1.5 mmol) and m-anisaldehyde (3ae, 0.120 mL, 1 mmol) afforded, after purification by flash chromatography [50 mL SiO2, Following the general procedure K, the reaction performed with iodobenzene 1v, pp.8-157
, 158 mL, 1.5 mmol) or 4-bromoanisole 1k (0.190 mL, 1.5 mmol) and p-anisaldehyde 3ae (0.120 mL, 1 mmol) or benzaldehyde 3j (0.106 mL, 1 mmol) afforded, after purification by flash chromatography [50 mL SiO2, Following the general procedure K, the reaction performed with bromobenzene 1a 69% or 99%) as a yellow solid, pp.8-159
, Following the general procedure K, the reaction performed with 4-bromobenzotrifluoride 1r (0.210 mL, 1.5 mmol) and m-anisaldehyde 3ae (0.100 mL, 1 mmol) afforded, after purification by flash chromatography [50 mL SiO2, 30%) as a yellow oil, pp.8-85
, 377 MHz, CDCl3): -62.5 (s, 3F)
, Following the general procedure K, the reaction performed with 2-bromoanisole 1i (0.190 mL, 1.5 mmol) and 2-thiophenecarboxaldehyde 3o (0.09 mL, 1 mmol) afforded, after purification by flash chromatography [50 mL SiO2, 72%) as a yellow oil, p.8
, 10 mmol) were successively added and the suspension was heated to reflux using a heat gun and then cooled down to rt Cobalt (II) bromide (22 mg, 0.1 mmol), 1,2-bis(diphenylphosphino)ethane (40 mg, 0.1 mmol) were added and the mixture was stirred for a few minutes at room temperature Halogenated aldehyde 9 (1 mmol) and Michael acceptor 2 (2.0 mmol) were successively added and the tube was sealed. The reaction was stirred at 80 °C (external temperature) for 16 h. Then, the reaction mixture was poured into sat. aq. NH4Cl (20 mL) and the resulting solution was extracted with EtOAc (3x20 mL) The combined organic layers were washed with brine, mL), trimethylsilyl chloride (10 ?L, p.2
, 206 mL, 2 mmol) and 2'-bromoacetophenone 10c (0.135 mL, 1 mmol) afforded, after purification by flash chromatography [100 mL SiO2, 50%) as a yellow oil, pp.11-101
, 400 mL)], 11g (227 mg or 242 mg, d.r.=77/23, 63% or 67%) as a white solid, pp.109-111
, 10 mmol) were successively added and the suspension was heated to reflux using a heat gun and then cooled down to rt Cobalt (II) bromide (22 mg, 0.1 mmol), 1,10-phenanthroline (18 mg, 0.1 mmol) were added and the mixture was stirred for a few minutes at room temperature mmol) and sulfonamide (1 mmol) were successively added and the tube was sealed. The reaction was stirred at 80 °C (external temperature) for 16 h. Then, the reaction mixture was poured into sat. aq. NH4Cl (20 mL) and the resulting solution was extracted with EtOAc (3x20 mL) The combined organic layers were washed with brine, trifluoroacetic acid (8 ?L, p.2, 2002.
, 117 mL, 1 mmol) or 2-chlorobenzaldehyde 9b (0.113 mL, 1 mmol) and p-toluenesulfonamide (171 mg, 1 mmol) afforded, after purification by flash chromatography [50 mL SiO2, pp.2-10
, 250 mL)], 11i (92 mg, 29%) as a white solid, 2CR reactions Other reactions Barbier reactions