Nitric Acid → HCID 69031897, compound

HRID 1830965Notes

Reaction equation

HRID 1830965 reaction equation
[N+](O)([O-])=O.[OH:5][C@H:6]1[C@@H:12]2[CH2:13][CH2:14][CH2:15][N:11]2[C:10](=[O:16])[C:9]2[CH:17]=[CH:18][CH:19]=[C:20](OC)[C:8]=2[N:7]1[C:23]([O:25][CH2:26][C:27]([Cl:30])([Cl:29])[Cl:28])=[O:24].[CH2:31]([O:34]C(N1C[C@H](O)C[C@H]1CO[Si](C(C)(C)C)(C)C)=O)C=C.[CH2:52]([O:59]C(N1C[C@H](O)C[C@H]1C(O)=O)=O)C1C=CC=CC=1>C(Cl)(Cl)Cl>[CH3:31][O:34][C:19]1[C:18]([O:59][CH3:52])=[CH:17][C:9]([C:10]([N:11]2[CH2:15][CH2:14][CH2:13][CH:12]2[CH2:6][OH:5])=[O:16])=[C:8]([NH:7][C:23]([O:25][CH2:26][C:27]([Cl:28])([Cl:30])[Cl:29])=[O:24])[CH:20]=1

Participants

6

Reactant 4

HCID 944Nitric Acid2×HCID 3915171-(Phenylmethyl) (2S,4R)-4-hydroxy-1,2-pyrrolidinedicarboxylateHCID 18639173(2S,4R)-1-allyloxycarbonyl-2-t-butyldimethylsilyloxymethyl-4-hydroxypyrrolidineHCID 86588596HCID 86588596, compound

Product 1

HCID 69031897HCID 69031897, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

Oxalyl chloride (0.38 mL, 4.33 mmol) was added to the crude Troc-protected anthranilic acid, prepared in the previous reaction, together with 2 drops of dry DMF in dry dichloromethane (30 mL). After initial strong effervescence, the mixture was allowed to stir at room temperature overnight. The resulting acid chloride was added dropwise, over 30 minutes, to a solution of 2S-(+)-pyrrolidinemethanol (0.44 g, 4.33 mmol) and TEA (1.37 ml, 9.85 mmol) of dry dichloromethane (15 mL) at −16° C. The reaction mixture was diluted with ethyl acetate (20 mL), and washed with dilute HCl (1N, 2×30 mL), satd. aqueous NaHCO3 (2×30 mL), water (30 mL) and brine (30 mL). The organic layer was then dried over MgSO4 and evaporated to give a yellow oil. The crude product was purified by flash chromatography (petroleum ether/ethyl acetate=50/50) to yield the product (1.2 g, 70%) as a pale yellow oil: 1H NMR (270 MHz, CDCl3) δ1.75 (m, 2H); 1.92 (m, 1H); 2.17 (m, 1H); 3.53 (m, 2H); 3.72 (m, 1H); 3.86 (s, 3H); 3.93 (s, 3H); 4.19 (m, 1H); 4.43 (m, 1H); 4.77 (d, J=12 Hz, 1H); 4.85 (d, J=12 Hz, 1H); 6.85 (s, 1H); 7.69 (s, 1H); 9.08 (bs, 1H). 13C NMR (67.8 MHz, CDCl3) δ25.1; 28.2; 51.4; 56.0; 56.4; 60.8; 65.9; 74.4; 95.3; 104.7; 110.7; 116.3; 130.8; 144.4; 151.0; 152.1; 170.4. MS: m/e (relative intensity) 454 (M−1, 5), 356 (3), 306 (10), 275 (5), 206 (100), 179 (15), 150 (10), 136 (3), 70 (45). HRMS Calculated for C17H21C13N2O6: 454.0465. Found: 454.0464. [α]25D=−72.2° (c=0.18, CHCl3).

Sources & evidence

ORD record
ord-5e29368f40ac442db9b33514b780cb7b
Source dataset
uspto-grants-2006_06
Patent number
US07067511B2

Reaction notes

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