(2S,4R)-1-allyloxycarbonyl-4-hydroxy-2-hydroxymethylpyrrolidine → 1-(Phenylmethyl) (2S,4R)-4-hydroxy-1,2-pyrrolidinedicarboxylate

HRID 915711Notes

Reaction equation

HRID 915711 reaction equation
C(OC(N1C[C@H:10](O)[CH2:9][C@H:8]1[CH2:13]O[Si](C(C)(C)C)(C)C)=O)C=C.C(OC1C=C(OC)C(C(N2CC(=C)CC2CO[Si](C(C)(C)C)(C)C)=O)=CC=1[N+]([O-])=O)CCOC1C=C(OC)C(C(N2CC(=C)CC2CO[Si](C(C)(C)C)(C)C)=O)=CC=1[N+]([O-])=O.[CH2:83]([O:86][C:87]([N:89]1[CH2:93][C@H:92]([OH:94])[CH2:91][C@H:90]1[C:95]([OH:97])=[O:96])=[O:88])[CH:84]=[CH2:85].C(OC(N1C[C@H](O)C[C@H]1CO)=O)C=C.NC1C=CC(I)=CC=1C(N1CC(=C)C[C@H]1CO)=O>CO>[CH2:83]([O:86][C:87]([N:89]1[CH2:93][C@H:92]([OH:94])[CH2:91][C@H:90]1[C:95]([OH:97])=[O:96])=[O:88])[C:84]1[CH:10]=[CH:9][CH:8]=[CH:13][CH:85]=1

Participants

7

Reactant 5

HCID 15086219(2S,4R)-1-allyloxycarbonyl-4-hydroxy-2-hydroxymethylpyrrolidineHCID 18639171(2S,4R)-1-allyloxycarbonyl-2-carboxy-4-hydroxypyrrolidineHCID 18639173(2S,4R)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-hydroxypyrrolidineHCID 69463669(2S)-N-(2-Amino-5-iodobenzoyl)-2-(hydroxymethyl)-4-methylidenepyrrolidineHCID 131726584[[(Propane-1,3-diyl)dioxy]bis[(2-nitro-5-methoxy-1,4-phenylene)carbonyl]]bis[2-(tert-butyldimethylsilyloxymethyl)-4-methylidenepyrrolidine]

Product 1

HCID 3915171-(Phenylmethyl) (2S,4R)-4-hydroxy-1,2-pyrrolidinedicarboxylate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of benzyl chloroformate (12.5 mL, 87.7 mL) in toluene (40 mL) was added to a solution of trans-4-hydroxy-L-proline 1 (10 g, 76.3 mmol) and NaHCO3 (16 g, 190 mmol) in H2O (165 mL) over a period of 15 minutes. After stirring at room temperature for 12 hours the two phases were allowed to separate. The aqueous phase was washed with diethyl ether (4×50 mL), cooled in an ice bath, and then acidified to pH 2 with conc. HCl. The resultant product was extracted with ethyl acetate (5×50 mL) and the combined organic extracts were dried (MgSO4) and the excess solvent evaporated in vacuo to afford a colourless viscous oil (20.30 g, 100%). [α]27D=−565° (c=0.1, MeOH). 1H NMR (CDCl3): δ 2.07-2.31 (m, 3H, H1), 3.52-3.59 (m, 2H, H3), 4.43-4.53 (m, 2H, H2,H11a), 5.8 and 5.11 (s, 2H, minor and major rotamers of H6, 1:2), 6.0 (bs, 2H, OH), 7.26-7.29 and 7.32-7.34 (m, 5H, minor and major rotamers of H arom, 1:2). IR (thin film): v=3414 (OH), 2940 (OH), 1682 (C═O), 1495, 1429, 1359 (CO2-), 1314, 1269, 1205, 1180, 1174, 1127, 1082, 1051, 993, 914, 866, 826, 769, 741, 697 cm−1. MS (EI): m/e (relative intensity): 266 (M+, 1), 265 (6), 220 (5), 176 (15), 130 (34), 108 (2), 91 (100), 86 (4), 68 (11). HRMS calcd. for C13H15NO5=265.0950 found 265.0976.

Sources & evidence

ORD record
ord-849017d73d7b4491916b1adab030ae48
Source dataset
uspto-grants-2007_09
Patent number
US07265105B2

Reaction notes

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