[3-(bromomethyl)phenyl]-trimethylsilane

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

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry 250 mL 3-necked flask equipped with a magnetic stirrer and a nitrogen inlet was charged with 2.08 g of t-butyl (2R, 3S)-(-)-6-oxo-2,3-diphenyl-4-morpholinecarboxylate (Aldrich), 1.43 g of 3-(trimethylsilyl)benzyl bromide (Yamakawa, T., et al, J. Med. Chem., 1990, 33, 1430), and 45 mL of anhydrous THF. The solution was cooled to -78° C. and was treated with 6.17 mL of 1 M sodium bis(trimethylsilyl)amide/THF (Aldrich) via syringe through a rubber septum. The solution was stirred at -78° C. for 3.5 h and was then poured into 150 mL of water. The resulting mixture was extracted with EtOAc (4×50 mL). The combined EtOAc extracts were washed with saturated brine (3×100 mL), dried over anhydrous Na2SO4, and concentrated in vacuo to give a light yellow oil. The crude material was purified by flash chromatography on silica gel (9:1 hexane:EtOAc) to afford 2.6 g (88%) of tert-butyl (2R, 3S, 5S)-6-oxo-2,3-diphenyl-5-(3-(trimethylsilyl)benzyl)-4-morpholinecarboxylate as a white powder, m.p. 88-90° C. A dry 250 mL 3-necked flask equipped with a magnetic stirrer and a nitrogen inlet The resulting mixture was extracted with EtOAc (4×50 mL) The combined EtOAc extracts were washed with saturated brine (3×100 mL) dried over anhydrous Na2SO4 concentrated in vacuo to give a light yellow oil The crude material was purified by flash chromatography on silica gel (9:1 hexane:EtOAc)

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

Procedure: A solution of 730 mg (3.00 mmol) of m-trimethylsilylbenzyl bromide and 1.18 g (4.50 mmol) of triphenylphosphine in 10 ml of dry toluene was refluxed for 4.5hours in an atmosphere of argon (125°-135° C. by oil bath). The precipitate was collected by filtration, and washed with toluene to give 1.361 g of white crystals, which were dried in vacuo (yield 90%). The precipitate was collected by filtration washed with toluene

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

Procedure: A solution of 730 mg (3.00 mmol) of m-trimethylsilylbenzyl bromide and 1.18 g (4.50 mmol) of triphenylphosphine in 10 ml of dry toluene was refluxed for 4.5 hours in an atmosphere of argon (125°-135° C. by oil bath). The precipitate was collected by filtration, and washed with toluene to give 1.361 g of white crystals, which were dried in vacuo (yield 90%). The precipitate was collected by filtration washed with toluene

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

Procedure: A solution of 730 mg (3.00 mmol) of m-trimethylsilylbenzyl bromide and 1.18 g (4.50 mmol) of triphenylphosphine in 10 ml of dry toluene was refluxed for 4.5 hours in an atmosphere of argon (125°-135° C. by oil bath). The precipitate was collected by filtration, and washed with toluene to give 1.361 g of white crystals, which were dried in vacuo (yield 90%). The precipitate was collected by filtration washed with toluene

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry 250 ml 3-necked flask equipped with a magnetic stirrer and a nitrogen inlet was charged with 2.08 g of t-butyl (2R, 3S)-(−)-6-oxo-2,3-diphenyl-4-morpholinecarboxylate (Aldrich), 1.43 g of 3-(trimethylsilyl)benzyl bromide (Yamakawa, T., et al, J. Med. Chem., 1990, 33, 1430), and 45 mL of anhydrous THF. The solution was cooled to −780° C. and was treated with 6.17 mL of 1 M sodium bis(trimethylsilyl)amide/THF (Aldrich) via syringe through a rubber septum. The solution was stirred at −78° C. for 3.5 h and was then poured into 150 mL of water. The resulting mixture was extracted with EtOAc (4×50 mL). The combined EtOAc extracts were washed with saturated brine (3×50 mL), dried over anhydrous Na2SO4, and concentrated in vacuo to give a light yellow oil. The crude material was purified by flash chromatography on silica gel (9:1 hexane:EtOAc) to afford 2.6 g (88%) of tert-butyl (2R, 3S, 5S)-6-oxo-2,3-diphenyl-5-(3-(trimethylsilyl)benzyl)-4-morpholinecarboxylate as a white powder, m.p. 88-90° C. A dry 250 ml 3-necked flask equipped with a magnetic stirrer and a nitrogen inlet The solution was cooled to −780° C. The resulting mixture was extracted with EtOAc (4×50 mL) The combined EtOAc extracts were washed with saturated brine (3×50 mL) dried over anhydrous Na2SO4 concentrated in vacuo to give a light yellow oil The crude material was purified by flash chromatography on silica gel (9:1 hexane:EtOAc)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry 250 mL 3-necked flask equipped with a magnetic stirrer and a nitrogen inlet was charged with 2.08 g of t-butyl (2R, 3S)-(-)-6-oxo-2,3-diphenyl-4-morpholinecarboxylate (Aldrich), 1.43 g of 3-(trimethylsilyl)benzyl bromide (Yamakawa, T., et al, J. Med. Chem., 1990, 33, 1430), and 45 mL of anhydrous THF. The solution was cooled to -78° C. and was treated with 6.17 mL of 1 M sodium bis(trimethylsilyl)amide/THF (Aldrich) via syringe through a rubber septum. The solution was stirred at -78° C. for 3.5 h and was then poured into 150 mL of water. The resulting mixture was extracted with EtOAc (4×50 mL). The combined EtOAc extracts were washed with saturated brine (3×100 mL), dried over anhydrous Na2SO4, and concentrated in vacuo to give a light yellow oil. The crude material was purified by flash chromatography on silica gel (9:1 hexane:EtOAc) to afford 2.6 g (88%) of tert-butyl (2R, 3S, 5S)-6-oxo-2,3-diphenyl-5-(3-(trimethylsilyl)benzyl)-4-morpholinecarboxylate as a white powder, m.p. 88-90° C. A dry 250 mL 3-necked flask equipped with a magnetic stirrer and a nitrogen inlet The resulting mixture was extracted with EtOAc (4×50 mL) The combined EtOAc extracts were washed with saturated brine (3×100 mL) dried over anhydrous Na2SO4 concentrated in vacuo to give a light yellow oil The crude material was purified by flash chromatography on silica gel (9:1 hexane:EtOAc)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry 250 mL 3-necked flask equipped with a magnetic stirrer and a nitrogen inlet was charged with 2.08 g of t-butyl (2R, 3S)-(-)-6-oxo-2,3-diphenyl-4-morpholinecarboxylate (Aldrich), 1.43 g of 3-(trimethylsilyl)benzyl bromide (Yamakawa, T., et al, J. Med. Chem., 1990, 33, 1430), and 45 mL of anhydrous THF. The solution was cooled to -78° C. and was treated with 6.17 mL of 1 M sodium bis(trimethylsilyl)amide/THF (Aldrich) via syringe through a rubber septum. The solution was stirred at -78° C. for 3.5 h and was then poured into 150 mL of water. The resulting mixture was extracted with EtOAc (4×50 mL). The combined EtOAc extracts were washed with saturated brine (3×100 mL), dried over anhydrous Na2SO4, and concentrated in vacuo to give a light yellow oil. The crude material was purified by flash chromatography on silica gel (9:1 hexane:EtOAc) to afford 2.6 g (88%) of tert-butyl (2R, 3S, 5S)-6-oxo-2,3-diphenyl-5-(3-(trimethylsilyl)benzyl)-4-morpholinecarboxylate as a white powder, m.p. 88-90° C. A dry 250 mL 3-necked flask equipped with a magnetic stirrer and a nitrogen inlet The resulting mixture was extracted with EtOAc (4×50 mL) The combined EtOAc extracts were washed with saturated brine (3×100 mL) dried over anhydrous Na2SO4 concentrated in vacuo to give a light yellow oil The crude material was purified by flash chromatography on silica gel (9:1 hexane:EtOAc)

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

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

Procedure: A mixture of 3-trimethylsilyltoluene (3.28 g, 10 mmol), N-bromosuccinimide (1.78 g, 10 mmol) and benzoylperoxide (10 mg) in CCl4 (20 ml) was stirred under reflux for 3 hours, then cooled and filtered. The solvent was removed under reduced pressure and 3-trimethylsilylbenzylbromide was purified by distillation. under reflux for 3 hours cooled filtered The solvent was removed under reduced pressure and 3-trimethylsilylbenzylbromide was purified by distillation

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of diethyl methylphosphonate (2.28 g, 15 mmol) in THF (20 ml) was added n-butyllithium (17 mmol, 1.6 M solution in hexane) at −78° C. After 45 min, the white suspension was added to a solution of the bromide 37 (3.65 g, 15 mmol) in THF (20 ml) and the mixture was stirred for 1.5 h. The temperature was then increased to −10° C. and after 1 h the deeply red colored solution was quenched by addition of saturated NH4Cl (aq). Volatiles were removed under reduced pressure and the residue was purified by flash chromatography (silica, EtOAc) to give 2.48 g (53%) of 38 as a colorless liquid. IR (film): 3473, 2955, 1248, 1058 and 1031; 1H NMR (200 MHz, CDCl3): δ0.30 (9H, s), 1.31 (6H, t, J=7 Hz), 2.10 (2H, m), 2.92 (2H, m), 4.11 (4H, m) and 7.29 (4H, m); 13C NMR (50 MHz, CDCl3): δ−1.2, 16.4, 26.3, 28.6, 29.0, 61.5, 127.9, 128.4, 131.2, 132.9, 139.9, 140.2 and 140.7; HR-MS (EI): e/m 314.1453 (M+C15H27O3PSi requires 314.1467). was quenched by addition of saturated NH4Cl (aq) Volatiles were removed under reduced pressure the residue was purified by flash chromatography (silica, EtOAc)

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

Procedure: A mixture of m-trimethylsilyltoluene (8.22 g, 50 mmol), NBS (8.90 g, 50 mmol), AIBN (0.05 g) and chlorobenzene (50 ml) was heated by means of a heating bath preheated to 110° C. An exothermic reaction started when the reaction mixture reached 80-90° C. and the orange suspension became a colorless solution within minutes. The mixture was cooled down with the aid of an ice-bath, ice water was added and the resulting mixture was extracted with hexane. The organic phase was washed with water, then brine and dried (MgSO4). Filtration through a silica plug (10 g) followed by evaporation of solvents yielded 12.05 g (99%) of 37 as a colorless liquid. Spectroscopic data were identical to those reported in the literature.43 was heated by means of a heating bath preheated to 110° C An exothermic reaction reached 80-90° C. The mixture was cooled down with the aid of an ice-bath the resulting mixture was extracted with hexane The organic phase was washed with water brine and dried (MgSO4) Filtration through a silica plug (10 g) followed by evaporation of solvents