Triphenylphosphine → dimethyl (S)-4-[1-(tert-butoxycarbonyl)-2-pyrrolidinylmethoxy]isophthalate

HRID 350362Notes

Reaction equation

HRID 350362 reaction equation
[OH:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[C:12]([O:14][CH3:15])=[O:13].[C:16]([N:23]1[CH2:29][CH2:28][CH2:27][C@H:24]1[CH2:25]O)([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[C:19]([O:18][C:16]([N:23]1[CH2:29][CH2:28][CH2:27][C@H:24]1[CH2:25][O:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[C:12]([O:14][CH3:15])=[O:13])=[O:17])([CH3:22])([CH3:20])[CH3:21]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 80087Dimethyl 4-hydroxyisophthalateHCID 643448(S)-(-)-N-Boc-prolinolHCID 5363146Diisopropyl azodicarboxylate

Product 1

HCID 86595076dimethyl (S)-4-[1-(tert-butoxycarbonyl)-2-pyrrolidinylmethoxy]isophthalateYield 88.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of dimethyl 4-hydroxyisophthalate (1.27 g, 6.04 mmol), (S)-N-Boc-Prolinol (1.22 g, 6.06 mmol), PPh3 (1.90 g, 7.24 mmol) in THF (30 mL) was added DIAD (1.43 mL, 7.26 mmol)at room temp. The resulting stirred mixture was then heated under reflux for 15 hr. After cooling to room temp, the resulting mixture was evaporated and the residue was purified by column chromatography on silica-gel with n-hexane-EtOAc (3:1, v/v) as eluent to give 2.10 g (88%) dimethyl (S)-4-[1-(tert-butoxycarbonyl)-2-pyrrolidinylmethoxy]isophthalate as a yellow oil. 1H-NMR (CDCl3) δ 1.26 (s, 9 H), 1.85–2.16 (m, 3 H), 3.36–3.46 (m, 2 H), 3.90 (s, 6 H), 4.11–4.31 (m, 2 H), 4.95–5.02 (m, 2 H), 7.09 (dd, H, J=9.3, 24.9 Hz), 8.11–8.14 (m, 1 H), 8.46 (d, 1 H, J=9.3 Hz)

Workup

  1. temperaturewas then heated
  2. temperatureunder reflux for 15 hr
  3. customthe resulting mixture was evaporated
  4. customthe residue was purified by column chromatography on silica-gel with n-hexane-EtOAc (3:1

Sources & evidence

ORD record
ord-8164dad0f6064a08bf517d1317a30169
Source dataset
uspto-grants-2007_02
Patent number
US07179819B2

Reaction notes

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