3-[tert-butyl(dimethyl)silyl]oxy-4-methoxybenzaldehyde

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

Procedure: To a cooled solution of 3-[(tert-Butyldimethylsilyl)oxy]-4-methoxybenzaldehyde 13 (17.5 g, 65.7 mmol) in methanol (100 mL) under nitrogen, sodium borohydride (2.98 g, 78.8 mmol) was added and stirred at room temperature for 30 min. After the reaction was complete as indicated by TLC (chloroform on silica gel plate), ice was added to the reaction mixture and extracted with ethyl acetate. The organic layer was separated, washed with water and dried. Removal of solvent in vacuo yielded on yellow oil 14 (73.5%). 1H NMR: δ 0.18 (s, 6H, 2×CH3), 1.00 (s, 9H, 3×CH3), 1.90 (br s, 1H, OH), 3.82 (s, 3H, OCH3), 4.56 (s, 2H, CH2OH), 6.94 (br s, 3H, Ar—H). Anal. Calcd for C14H24O3Si: C, 62.64, H, 9.01. Found: C, 62.59, H, 9.03. was added to the reaction mixture extracted with ethyl acetate The organic layer was separated washed with water dried Removal of solvent in vacuo

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

Procedure: To a cooled solution of 3-[(tert-Butyldimethylsilyl)oxy]-4-methoxybenzaldehyde 13 (17.5 g, 65.7 mmol) in methanol (100 mL) under nitrogen, sodium borohydride (2.98 g, 78.8 mmol) was added and stirred at room temperature for 30 min. After the reaction was complete as indicated by TLC (chloroform on silica gel plate), ice was added to the reaction mixture and extracted with ethyl acetate. The organic layer was separated, washed with water and dried. Removal of solvent in vacuo yielded on yellow oil 14 (73.5%). 1H NMR: δ 0.18 (s, 6H, 2×CH3), 1.00 (s, 9H, 3×CH3), 1.90 (br s, 1H, OH), 3.82 (s, 3H, OCH3), 4.56 (s, 2H, CH2OH), 6.94 (br s, 3H, Ar—H). Anal. Calcd for C14H24O3Si: C, 62.64, H, 9.01. Found: C, 62.59, H, 9.03. was added to the reaction mixture extracted with ethyl acetate The organic layer was separated washed with water dried Removal of solvent in vacuo

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

Procedure: To a cooled solution of 3-hydroxy-4-methoxybenzaldehyde 12 (10.0 g, 65.7 mmol) in dry N,N-dimethyl formamide (75 mL) was added diisopropylethylamine (16.99 g, 131.4 mmol). Before the addition of 1.0 M solution of tert-butyldimethylsilyl chloride in tetrahydrofuran (11.89 g or 78.9 mL, 78.85 mmol) the mixture was stirred under nitrogen for 10 min. After complete addition over 30 min, the reaction mixture was left overnight (12-16 h). Reaction completion was checked by TLC (chloroform on silica gel plate). Water was added to the reaction mixture, extracted with dichloromethane and the organic layer was washed with a saturated sodium bicarbonate solution, water and dried. Removal of solvent in vacuo yielded as an oil which was subjected to column chromatography (eluant: chloroform) to afford as an yellow viscous oil 13 (100%). 1H NMR: δ 0.21 (s, 6H, 2×CH3), 1.01 (s, 9H, 3×CH3), 3.91 (s, 3H, OCH3), 6.94 (d, 1H, J=8.5 Hz, 5H), 7.36 (d, 1H, J=2 Hz, 2H), 7.47 (dd, 1H, J=8.5, 2 Hz, 6H), 9.89 (s, 1H, CHO). Anal. Calcd for C14H22O3Si: C, 63.12, H, 8.32. Found: C, 63.09, H, 8.30. After complete addition over 30 min the reaction mixture was left overnight (12-16 h) Reaction completion extracted with dichloromethane the organic layer was washed with a saturated sodium bicarbonate solution, water dried Removal of solvent in vacuo yielded as an oil which

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

Procedure: Prepared as in Example 12-1b from 3-(tert-butyldimethylsilyloxy)-4-methoxybenzaldehyde (Example 12-2c) and methyl 1-aminocyclopropanecarboxylate hydrochloride. Yield 79%. MS 366 (MH+).

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

Procedure: Prepared as in Example 12-1b from 3-(tert-butyldimethylsilyloxy)-4-methoxybenzaldehyde (Example 12-2c) and methyl 1-aminocyclopropanecarboxylate hydrochloride. Yield 79%. MS 366 (MH+).

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

Procedure: Prepared as in Example 12-1c from 3-hydroxy-4-methoxybenzaldehyde and tert-butylchlorodimethylsilane. Yield 100%, yellowish liquid. MS 267 (MH+).

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

Procedure: Prepared as in Example 12-1b from 3-(tert-butyldimethylsilyloxy)-4-methoxybenzaldehyde (Example 12-2c) and ethyl 2-amino-2-methylpropanoate hydrochloride. Yield 94%, colorless liquid. MS 382 (MH+).

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

Procedure: Prepared as in Example 12-1b from 3-(tert-butyldimethylsilyloxy)-4-methoxybenzaldehyde (Example 12-2c) and methyl 1-aminocyclopropanecarboxylate hydrochloride. Yield 79%. MS 366 (MH+).

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

Procedure: Prepared as in Example 12-1b from 3-(tert-butyldimethylsilyloxy)-4-methoxybenzaldehyde (Example 12-2c) and methyl 1-aminocyclopropanecarboxylate hydrochloride. Yield 79%. MS 366 (MH+).

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

Procedure: Prepared as in Example 12-1c from 3-hydroxy-4-methoxybenzaldehyde and tert-butylchlorodimethylsilane. Yield 100%, yellowish liquid. MS 267 (MH+).

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

Procedure: Prepared as in Example 12-1b from 3-(tert-butyldimethylsilyloxy)-4-methoxybenzaldehyde (Example 12-2c) and ethyl 2-amino-2-methylpropanoate hydrochloride. Yield 94%, colorless liquid. MS 382 (MH+).

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

Procedure: Prepared as in Example 12-1c from 3-hydroxy-4-methoxybenzaldehyde and tert-butylchlorodimethylsilane. Yield 100%, yellowish liquid. MS 267 (MH+).