Pivaloyl chloride → HCID 21967605, compound

HRID 1637420Notes

Reaction equation

HRID 1637420 reaction equation
[N:1]([C@@H:4]1[C@H:16]([O:17][C:18](=[O:25])[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C@H:15]([CH3:26])[O:14][C@H:6]([S:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[C@H:5]1[OH:27])=[N+:2]=[N-:3].[C:28](Cl)(=[O:33])[C:29]([CH3:32])([CH3:31])[CH3:30]>CN(C1C=CN=CC=1)C.C(Cl)Cl>[N:1]([C@@H:4]1[C@H:16]([O:17][C:18](=[O:25])[C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)[C@H:15]([CH3:26])[O:14][C@H:6]([S:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[C@H:5]1[O:27][C:28](=[O:33])[C:29]([CH3:32])([CH3:31])[CH3:30])=[N+:2]=[N-:3]

Participants

5

Reactant 2

HCID 62493Pivaloyl chlorideHCID 21967603HCID 21967603, compound

Product 1

HCID 21967605HCID 21967605, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of phenyl 3-azido-4-O-benzoyl-3,6di-deoxy-1-thio-β-L-galactopyranoside (β-18) (118 mg, 0.307 mmol) in 5 mL of CH2C2 is added TEA (256 μL, 1.87 mmol), pivaloyl chloride (114 μL, 0.921 mmol) and DMAP (19 mg, 0.154 mmol). The reaction mixture is stirred at room temperature for 12 h, diluted with 15 mL of CH2Cl2, washed with 1M HCl (2×10 mL), dried over Na2SO4, filtered and concentrated. The crude product is purified by flash chromatography (20% EtOAc/petroleum ether) to give 114 mg (80%) of phenyl 3-azido-4-O-benzoyl-3,6-di-deoxy-2-O-pivaloyl-1-thio-β-L-galactopyranoside (β-19): Rf 0.54 (20% EtOAc/petroleum ether); 1H NMR (CDCl3, 270 MHz) δ 7.93 (d, 2H, ArH), 7.59-7.56 (m, 3H, ArH), 7.46-7.26 (m, 5H, ArH), 5.53 (d, J=2.6 Hz, 1H, H-4), 5.25 (t, J=9.9 Hz, 1H, H-2) 4.73 (d, J=9.9 Hz, 1H, H-1), 3.92 (q, J=6.3 Hz, 1H, H-5), 3.79 (dd, J=2.6, 9.9 Hz, 1H, H-3), 1.42-1.21 (m, 12H, H-6, CH3); 13C NMR (CDCl3, 68 MHz) δ 176.8, 165.9, 133.8, 133.7, 131.8, 130.2, 129.0, 128.9, 128.6, 128.4, 86.1, 74.4, 71.6, 68.3, 63.9, 39.1, 27.3, 16.9; FAMS C24H27O5N3 (MNa+) calcd 492.1569, found 492.1579.

Workup

  1. washwashed with 1M HCl (2×10 mL)
  2. dry with materialdried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe crude product is purified by flash chromatography (20% EtOAc/petroleum ether)

Sources & evidence

ORD record
ord-d859c41f424a47b7831fe0d060051ae5
Source dataset
uspto-grants-2000_03
Patent number
US06040433

Reaction notes

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