تفاعل #7771

معادلة التفاعل

NH4Cl

BF3 Et2O

(±)(1S*,2R*,4S*)-4-(benzyloxy)-1,2-epoxycyclohexane

1-Methanesulfonyl-4-methylsulfanyl-benzene

nBuLi

→

(±)(1R*,2R*,5S*)-5-benzyloxy-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexanol

المردود 80.3%

المذيبات

THF

EtOAc

THF

ظروف التفاعل

المعالجة

1. 1
   workup.ADDITIONAfter an addition 1 h at −78° C.
2. 2
   درجة الحرارةthe solution was warmed to 0° C
3. 3
   workup.WAITAfter 2 h
4. 4
   درجة الحرارةthe solution was cooled to −78° C.
5. 5
   درجة الحرارةThe solution was warmed to rt
6. 6
   غسيلThe organic layer was washed with brine
7. 7
   أخرىdried
8. 8
   ترشيحfiltered
9. 9
   تركيزconcentrated

الإجراء التجريبي

1-Methanesulfonyl-4-methylsulfanyl-benzene (3.25 g) was dissolved in THF (50 mL) and cooled to −78° C. prior to the addition of 1.6 M nBuLi (10 mL). After 0.5 h, BF3-Et2O (2.04 mL) was added followed by (±)(1S*,2R*,4S*)-4-(benzyloxy)-1,2-epoxycyclohexane (2.19 g) (Chini et al. J. Org. Chem. 1990, 55, 4265) in THF (20 mL). After an addition 1 h at −78° C., the solution was warmed to 0° C. After 2 h, the solution was cooled to −78° C. and saturated NH4Cl solution (aq) was added. The solution was warmed to rt and EtOAc was added. The organic layer was washed with brine, dried, filtered, and concentrated. Flash chromatography of the resulting residue gave (±)(1R*,2R*,5S*)-5-benzyloxy-2-(4-methylsulfanyl-benzenesulfonylmethyl)-cyclohexanol (3.5 g) as the major product: 1H NMR (CDCl3, δ ppm, 300 mHz) 1.41 (m, 2H), 1.59 (m, 1H), 1.95 (m, 1H), 2.05-2.35 (m, 2H), 2.54 (s, 3H), 2.96 (dd, 1H), 3.64 (m, 2H), 3.81 (s, 1H), 4.48 (m, 2H), 7.3 (m, 7H), 7.82 (d, 2H)

المصدر