4-tri(propan-2-yl)silyloxybenzaldehyde

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: Heat at reflux a mixture of the aldehyde (2.1033 g, 7.55 mmol), p-TsOH.H2O (14.4 mg, 0.076 mmol), and ethylene glycol (4.2 mL, 75.5 mmol) in benzene (75 mL) overnight, while removing azeotropically the H2O formed. Cool and wash with 10% K2CO3 (2×50 mL) and brine which contains 10% K2CO3 (50 mL). Back-extract the aqueous layers with benzene and Et2O (100 mL each). Concentrate the combined organic layers after drying over Na2SO4 to afford (4-[1,3]dioxolan-2-yl-phenoxy)triisopropylsilane. Heat at reflux while removing azeotropically the H2O formed Cool wash with 10% K2CO3 (2×50 mL) and brine which Back-extract the aqueous layers with benzene and Et2O (100 mL each) Concentrate the combined organic layers after drying over Na2SO4

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

Procedure: Mix 4-hydroxybenzaldehyde (1.23 g, 10.1 mmol), imidazole (1.37 g, 20.2 mmol), and triisopropylsilyl chloride (2.60 mL, 12.1 mmol) in DMF (10 mL) and stir at room temperature for 2 hours. Quench the reaction with saturated aqueous NH4Cl (50 mL) and extract with EtOAc (3× 100 mL). Wash the organic layers with H2O and brine (50 mL each). Combine the organic layers, dry over MgSO4, concentrate and purify by flash chromatography, eluting with 2.5% Et2O/hexanes to afford 4-triisopropylsilyloxybenzaldehyde (2.78 g, 99%). Quench the reaction with saturated aqueous NH4Cl (50 mL) extract with EtOAc (3× 100 mL) Wash the organic layers with H2O and brine (50 mL each) Combine the organic layers, dry over MgSO4 concentrate purify by flash chromatography eluting with 2.5% Et2O/hexanes

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

Procedure: Mix 4-hydroxybenzaldehyde (1.23 g, 10.1 mmol), imidazole (1.37 g, 20.2 mmol), and triisopropylsilyl chloride (2.60 mL, 12.1 mmol) in DMF (10 mL) and stir at room temperature for 2 hours. Quench the reaction with saturated aqueous NH4Cl (50 mL) and extract with EtOAc (3× 100 mL). Wash the organic layers with H2O and brine (50 mL each). Combine the organic layers, dry over MgSO4, concentrate and purify by flash chromatography, eluting with 2.5% Et2O/hexanes to afford 4-triisopropylsilyloxybenzaldehyde (2.78 g, 99%). Quench the reaction with saturated aqueous NH4Cl (50 mL) extract with EtOAc (3× 100 mL) Wash the organic layers with H2O and brine (50 mL each) Combine the organic layers, dry over MgSO4 concentrate purify by flash chromatography eluting with 2.5% Et2O/hexanes

Conditions: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of trimethylethylenediamine (0.45 mL, 3.48 mmol) in THF (9 mL) at −20° C. was added Butyllithium 1.6M in hexanes (2.11 mL, 3.8 mmol). The solution was stirred at −20° C. for 15 min. A solution of 4-Triisopropylsilanyloxy-benzaldehyde (0.922 g, 3.31 mmol) was added dropwise and the solution stirred for 15 min at −20° C. Bu 16M in hexanes (6.21 ml, 9.93 mmol) was added dropwise and the solution kept in the freezer at −20° C. for 26 hours. The solution was cooled to 40° C. and methyl iodide (3.71 mL, 59.60 mmol) was added. The solution was allowed to reach room temperature and further stirred 30 ml. The reaction was quenched with saturated ammonium chloride (20 mL) and extracted with ethyl acetate (3×30 mL). The combined extracts were dried (MgSO4), concentrated under vacuum and purified by column chromatography (silica gel, hexanes/Ethyl acetate 20:1, Rf0.085) (49%). 1H-NMR (CDCl3, 200.15 MHz): δ 10.1 (s, 1H), 7.69 (d, 1H, J=8.3), 6.80 (dd, 1H,J=8.6, 2.4), 6.72 (s, 1H), 0.61 (s, 3H), 1.33–1.19 (m, 3H), 1.12 (s,18H). the solution stirred for 15 min at −20° C the solution kept in the freezer at −20° C. for 26 hours The solution was cooled to 40° C. to reach room temperature The reaction was quenched with saturated ammonium chloride (20 mL) extracted with ethyl acetate (3×30 mL) The combined extracts were dried (MgSO4) concentrated under vacuum purified by column chromatography (silica gel, hexanes/Ethyl acetate 20:1, Rf0.085) (49%)

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

Procedure: Heat at reflux a mixture of the aldehyde (2.1033 g, 7.55 mmol), p-TsOH.H2O (14.4 mg, 0.076 mmol), and ethylene glycol (4.2 mL, 75.5 mmol) in benzene (75 mL) overnight, while removing azeotropically the H2O formed. Cool and wash with 10% K2CO3 (2×50 mL) and brine which contains 10% K2CO3 (50 mL). Back-extract the aqueous layers with benzene and Et2O (100 mL each). Concentrate the combined organic layers after drying over Na2SO4 to afford (4-[1,3]dioxolan-2-yl-phenoxy)triisopropylsilane. Heat at reflux while removing azeotropically the H2O formed Cool wash with 10% K2CO3 (2×50 mL) and brine which Back-extract the aqueous layers with benzene and Et2O (100 mL each) Concentrate the combined organic layers after drying over Na2SO4

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

Procedure: Heat at reflux a mixture of the aldehyde (2.1033 g, 7.55 mmol), p-TsOH.H2O (14.4 mg, 0.076 mmol), and ethylene glycol (4.2 mL, 75.5 mmol) in benzene (75 mL) overnight, while removing azeotropically the H2O formed. Cool and wash with 10% K2CO3 (2×50 mL) and brine which contains 10% K2CO3 (50 mL). Back-extract the aqueous layers with benzene and Et2O (100 mL each). Concentrate the combined organic layers after drying over Na2SO4 to afford (4-[1,3]dioxolan-2-yl-phenoxy)triisopropylsilane. Heat at reflux while removing azeotropically the H2O formed Cool wash with 10% K2CO3 (2×50 mL) and brine which Back-extract the aqueous layers with benzene and Et2O (100 mL each) Concentrate the combined organic layers after drying over Na2SO4

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

Procedure: Mix 4-hydroxybenzaldehyde (1.23 g, 10.1 mmol), imidazole (1.37 g, 20.2 mmol), and triisopropylsilyl chloride (2.60 mL, 12.1 mmol) in DMF (10 mL) and stir at room temperature for 2 hours. Quench the reaction with saturated aqueous NH4Cl (50 mL) and extract with EtOAc (3×100 mL). Wash the organic layers with H2O and brine (50 mL each). Combine the organic layers, dry over MgSO4, concentrate and purify by flash chromatography, eluting with 2.5% Et2O/hexanes to afford 4-triisopropylsilyloxybenzaldehyde (2.78 g, 99%). Quench the reaction with saturated aqueous NH4Cl (50 mL) extract with EtOAc (3×100 mL) Wash the organic layers with H2O and brine (50 mL each) Combine the organic layers, dry over MgSO4 concentrate purify by flash chromatography eluting with 2.5% Et2O/hexanes

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

Procedure: Heat at reflux a mixture of the aldehyde (2.1033 g, 7.55 mmol), p-TsOH.H2O (14.4 mg, 0.076 mmol), and ethylene glycol (4.2 mL, 75.5 mmol) in benzene (75 mL) overnight, while removing azeotropically the H2O formed. Cool and wash with 10% K2CO3 (2×50 mL) and brine which contains 10% K2CO3 (50 mL). Back-extract the aqueous layers with benzene and Et2O (100 mL each). Concentrate the combined organic layers after drying over Na2SO4 to afford (4-[1,3]dioxolan-2-yl-phenoxy)triisopropylsilane. Heat at reflux while removing azeotropically the H2O formed Cool wash with 10% K2CO3 (2×50 mL) and brine which Back-extract the aqueous layers with benzene and Et2O (100 mL each) Concentrate the combined organic layers after drying over Na2SO4

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

Procedure: Heat at reflux a mixture of the aldehyde (2.1033 g, 7.55 mmol), p-TsOH.H2O (14.4 mg, 0.076 mmol), and ethylene glycol (4.2 mL, 75.5 mmol) in benzene (75 mL) overnight, while removing azeotropically the H2O formed. Cool and wash with 10% K2CO3 (2×50 mL) and brine which contains 10% K2CO3 (50 mL). Back-extract the aqueous layers with benzene and Et2O (100 mL each). Concentrate the combined organic layers after drying over Na2SO4 to afford (4-[1,3]dioxolan-2-yl-phenoxy)triisopropylsilane. Heat at reflux while removing azeotropically the H2O formed Cool wash with 10% K2CO3 (2×50 mL) and brine which Back-extract the aqueous layers with benzene and Et2O (100 mL each) Concentrate the combined organic layers after drying over Na2SO4