Isopropyl chloroformate → HCID 53378368, compound

HRID 1620427Notes

Reaction equation

HRID 1620427 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C@H:8]([N:13]1[CH2:18][CH2:17][CH:16]2[S:19][C:20](=[O:22])[CH:21]=[C:15]2[CH2:14]1)[C:9]([O:11][CH3:12])=[O:10].Cl[C:24]([O:26][CH:27]([CH3:29])[CH3:28])=[O:25].C(OC(OC1SC2CCN([C@@H](C3C=CC=CC=3Cl)C(OC)=O)CC=2C=1)=O)C(C)C>CO>[CH:27]([O:26][C:24]([O:22][C:20]1[S:19][C:16]2[CH2:17][CH2:18][N:13]([C@@H:8]([C:3]3[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=3[Cl:1])[C:9]([O:11][CH3:12])=[O:10])[CH2:14][C:15]=2[CH:21]=1)=[O:25])([CH3:29])[CH3:28]

Participants

5

Reactant 3

HCID 7917Isopropyl chloroformateHCID 53378367HCID 53378367, compoundHCID 56848893Methyl (2S)-(2-chlorophenyl)(2-oxo-2,6,7,7a-tetrahydrothieno[3,2-c]pyridin-5(4H)-yl)acetate

Product 1

HCID 53378368HCID 53378368, compoundYield 94%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Following the method described in Example 18, (2S)-methyl 2-(2-chlorophenyl)-2-(2-oxo-7,7a-dihydrothieno[3.2-c]pyridin-5(2H,4H,6H)-yl)-acetate (IV-1) (85 mg) was reacted with isopropyl chloroformate (0.23 ml), to prepare (S)-methyl 2-(2-(isobutoxycarbonyloxy)-6,7-dihydrothieno[3,2-c]pyridin-5(4H)-yl)-2-(2-chlorophenyl)-acetate (I-15) (100 mg). Yield: 94%, ee=97.5% (chiral HPLC analysis conditions were the same as those in Example 4), [α]D20=+34.00° (c 0.50, MeOH); 1H-NMR (300 MHz, CDCl3) δ 1.36 (d, 6H, J=6.2 Hz), 2.77-2.78 (m, 2H), 2.86-2.89 (m, 2H), 3.52 (d, 1H, J=14.2 Hz), 3.64 (d, 1H, J=14.3 Hz), 3.72 (s, 3H), 4.90 (s, 1H), 4.93-5.01 (m, 1H), 6.30 (s, 1H), 7.24-7.68 (m, 4H); 13C-NMR (75 MHz, CDCl3) δ 21.6, 25.4, 48.1, 50.3, 52.1, 67.8, 73.9, 112.2, 125.7, 127.1, 129.4, 129.8, 129.9, 130.3, 133.7, 134.7, 150.5, 152.0, 171.2; ESI-MS m/z 424.1 [M+H]+; HRMS Calcd for C20H23NO5SCl [M+H]+ m/z 424.0989. found 424.0985.

Sources & evidence

ORD record
ord-3465fec3bc3b4926a461be55187b5b3e
Source dataset
uspto-grants-2014_07
Patent number
US08772489B2

Reaction notes

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