تفاعل #332105

معادلة التفاعل

sodium hypochlorite

potassium bromide

sodium bicarbonate

(S)-3-hydroxymethyl-pyrrolidine-1-carboxylic acid t-butyl ester

→

(S)-3-formylpyrrolidine-1-carboxylic acid t-butyl ester

المردود 87.0%

المذيبات

water

DCM

ظروف التفاعل

المعالجة

1. 1
   workup.ADDITIONwas added
2. 2
   workup.STIRRINGAfter 15 minutes of stirring at 0° C.
3. 3
   أخرىin the 6-8° C. range
4. 4
   أخرىThe mixture was placed in an ice bath until the layers
5. 5
   أخرىseparated
6. 6
   أخرىThe organic layer was separated
7. 7
   استخلاصthe aqueous layer was extracted with DCM (200 mL)
8. 8
   غسيلThe combined organic layers were washed with saturated aqueous NaCl (200 mL)
9. 9
   تجفيفdried over Na2SO4
10. 10
    ترشيحfiltered
11. 11
    تركيزconcentrated

الإجراء التجريبي

A solution of (S)-3-hydroxymethyl-pyrrolidine-1-carboxylic acid t-butyl ester (25.0 g, 124 mmol, 1.0 eq.) in DCM (200 mL) was cooled with stirring to 0° C. A solution of potassium bromide (1.5 g, 12.4 mmol, 0.1 eq.) and sodium bicarbonate (1.5 g, 17.4 mmol, 0.14 eq.) dissolved in water (100 mL) was added. After 15 minutes of stirring at 0° C., TEMPO (195.3 mg, 1.2 mmol, 0.01 eq.) was added, followed by the slow addition of sodium hypochlorite (77.3 mL, 136.6 mmol, 1.1 eq.) dropwise keeping the internal temperature in the 6-8° C. range. The mixture was placed in an ice bath until the layers separated. The organic layer was separated and the aqueous layer was extracted with DCM (200 mL). The combined organic layers were washed with saturated aqueous NaCl (200 mL), dried over Na2SO4, filtered, and concentrated to yield crude (S)-3-formylpyrrolidine-1-carboxylic acid t-butyl ester (21.5 g).

المصدر