Methyl p-toluenesulfonate → 3-Pyrrolidinol, 1-[(4-methylphenyl)sulfonyl]-, 3-(4-methylbenzenesulfonate), (3S)-

HRID 1198457Notes

Reaction equation

HRID 1198457 reaction equation
[C:1]1([CH3:12])[CH:6]=[CH:5][C:4]([S:7]([O:10][CH3:11])(=[O:9])=[O:8])=[CH:3][CH:2]=1.[S:13]([N:23]1[CH2:27]C[C@@H:25](O)[CH2:24]1)([C:16]1[CH:22]=[CH:21][C:19]([CH3:20])=[CH:18][CH:17]=1)(=[O:15])=[O:14].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[S:13]([N:23]1[CH2:24][CH2:25][C@H:11]([O:10][S:7]([C:4]2[CH:3]=[CH:2][C:1]([CH3:12])=[CH:6][CH:5]=2)(=[O:9])=[O:8])[CH2:27]1)([C:16]1[CH:22]=[CH:21][C:19]([CH3:20])=[CH:18][CH:17]=1)(=[O:14])=[O:15]

Participants

6

Reactant 4

HCID 6645Methyl p-toluenesulfonateHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 16216944(3R)-1-(4-Methylbenzene-1-sulfonyl)pyrrolidin-3-ol

Product 1

HCID 442480203-Pyrrolidinol, 1-[(4-methylphenyl)sulfonyl]-, 3-(4-methylbenzenesulfonate), (3S)-

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

Methyl para-toluenesulphonate (54 g) was added in portions to a solution of 1-tosyl-3-(R)-(-)-hydroxypyrrolidine (49 g--see Preparation 2) and triphenylphosphine (76 g) in anhydrous tetrahydrofuran (700 ml) at 0° C. The mixture was cooled to -20° C. and diethyl azodicarboxylate (58 g--"DEAD") was added, dropwise, over 30 minutes. During this time, the temperature of the mixture was not allowed to rise above -10° C. When the addition was complete the mixture was allowed to warm to room temperature and stirred for 16 hours. The mixture was concentrated in vacuo to give a solid which was purified by column chromatography on silica eluting with hexane containing dichloromethane (50%). The product-containing fractions were combined and concentrated in vacuo to give an oil which was crystallised from 1-propanol to give the title compound as a colourless solid, yield 56 g, m.p. 110° C., [α]D25 -5.2° (c 1.0, CH2Cl2).

Workup

  1. customto rise above -10° C
  2. additionWhen the addition
  3. temperatureto warm to room temperature
  4. concentrationThe mixture was concentrated in vacuo
  5. customto give a solid which
  6. customwas purified by column chromatography on silica eluting with hexane
  7. additioncontaining dichloromethane (50%)
  8. concentrationconcentrated in vacuo
  9. customto give an oil which
  10. customwas crystallised from 1-propanol

Sources & evidence

ORD record
ord-3b7f574959804c71a49637013a045672
Source dataset
uspto-grants-1994_01
Patent number
US05281601

Reaction notes

Loading…