4-ethyl-3-iodobenzaldehyde

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Potassium hexamethyldisilazide (0.5 M in THF) (46.1 mL, 23.07 mmol) was added dropwise to a stirred suspension of methyltriphenylphosphohonium bromide (8.24 g, 23.1 mmol) in dry THF (62 mL) at 0° C. and the mixture was stirred for 20 min. A solution of 4-ethyl-3-iodobenzaldehyde (2.40 g, 9.23 mmol) in dry THF (31 mL) was added via cannula. The reaction mixture was allowed to warm to room temperature and stirred overnight. The reaction was quenched with satd NH4Cl (50 mL) and the resulting mixture was extracted with EtOAc (3×50 mL). The combined extracts were dried (MgSO4) and concentrated in vacuo to give the crude product. This was purified by flash chromatography (Biotage Horizon, 40M, Si, ˜30 mL/min, 100% hexanes for 2448 mL) to afford 4-ethenyl-1-ethyl-2-iodobenzene, as a colorless oil. Rf=0.79 (hexanes). 1H NMR (500 MHz, CDCl3): δ 7.37 (d, J=1.8 Hz, 1H); 6.83 (dd, J=7.9, 1.8 Hz, 1H); 6.68 (d, J=7.9 Hz, 1H); 6.11 (dd, J=17.6, 10.9 Hz, 1H); 5.21 (d, J=17.6 Hz, 1H); 4.72 (d, J=9.7 Hz, 1H); 2.23 (q, J=7.5 Hz, 2H); 0.72 (t, J=7.5 Hz, 3H). stirred overnight The reaction was quenched with satd NH4Cl (50 mL) the resulting mixture was extracted with EtOAc (3×50 mL) The combined extracts were dried (MgSO4) concentrated in vacuo to give the crude product This was purified by flash chromatography (Biotage Horizon, 40M, Si, ˜30 mL/min, 100% hexanes for 2448 mL)

Conditions: temp:27.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Iodine (0.245 mL, 4.73 mmol) and sodium metaperiodate (0.340 g, 1.59 mmol) were added slowly portionwise successively to stirred 95% H2SO4 (30.0 mL) at 25° C. and the mixture was stirred for 30 min to afford a dark brown iodinating solution. The iodinating solution was added dropwise to a stirred suspension of 4-ethylbenzaldehyde (1.34 g, 10 mmol) in 95% H2SO4 (10.0 mL) over 45 min while maintaining the temperature at 25-30° C. Stirring was continued for a further 15 min and the reaction was quenched by slowly pouring into stirred ice-water (300 mL). The precipitate was collected by filtration, washed with water and dried under vacuum to afford 4-ethyl-3-iodobenzaldehyde, as a colorless solid. 1H NMR (600 MHz, CDCl3): δ 9.87 (s, 1H); 8.28 (d, J=1.7 Hz, 1H); 7.77 (dd, J=7.8, 1.6 Hz, 1H); 7.36 (d, J=7.8 Hz, 1H); 2.78 (q, J=7.6 Hz, 2H); 1.23 (t, J=7.6 Hz, 4H). to afford a dark brown iodinating solution Stirring was continued for a further 15 min the reaction was quenched by slowly pouring into stirred ice-water (300 mL) The precipitate was collected by filtration washed with water dried under vacuum