Pivaloyl chloride → HCID 15460402, compound

HRID 1637416Notes

Reaction equation

HRID 1637416 reaction equation
[S:1]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C@H:2]1[O:10][C@@H:9]([CH3:11])[C@@H:7]([OH:8])[C@@H:5]([OH:6])[C@@H:3]1[OH:4].[C:18](Cl)(=[O:23])[C:19]([CH3:22])([CH3:21])[CH3:20]>N1C=CC=CC=1.CN(C1C=CN=CC=1)C.C(Cl)Cl>[C:18]([O:4][C@H:3]1[C@H:5]([O:6][C:18](=[O:23])[C:19]([CH3:22])([CH3:21])[CH3:20])[C@H:7]([O:8][C:18](=[O:23])[C:19]([CH3:22])([CH3:21])[CH3:20])[C@H:9]([CH3:11])[O:10][C@@H:2]1[S:1][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)(=[O:23])[C:19]([CH3:22])([CH3:21])[CH3:20]

Participants

6

Reactant 2

HCID 62493Pivaloyl chlorideHCID 54499710HCID 54499710, compound

Product 1

HCID 15460402HCID 15460402, compound

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of crude phenyl 6-deoxy-1-thio-β-L-galactopyranoside 3 in 15 mL of pyridine is added pivaloyl chloride (4.0 mL, 3.90 g, 32.5 mmol) and DMAP (0.33 g, 2.71 mmol). The reaction mixture is heated at 100° C. for 12 h, cooled, diluted with 50 mL of CH2Cl2, washed with H2O (100 mL) and saturated NaCl (100 mL), dried over Na2SO4, filtered and concentrated to afford 3.25 g of phenyl 6-deoxy-2,3,4-tri-O-pivaloyl-1-thio-β-L-galactopyranoside 4 as a brown oil. This oil is purified by flash chromatography (15% EtOAc/petroleum ether) to afford 0.53 g (48%) of the pure compound. An additional 0.81 g of a brown oil, which that appeared to be a mixture of incompletely acylated products, is also isolated. This material is resubjected to the reaction conditions for 48 h and provided an additional 0.21 g (19%, total yield 67% for 2 steps): Rf 0.48 (15% EtOAc/petroleum ether); 1H NMR (CDCl3, 270 MHz) δ 7.50-7.59 (m, 2H), 7.23-7.35 (m, 3H), 5.16-5.30 (m, 2H), 5.08 (dd, J=9.9, 3.0 Hz, 1H, H-3), 4.66 (d, J=9.6 Hz, 1H, H-1), 3.90 (q, J=6.3 Hz, 1H, H-5), 1.21 (s, 9H), 1.18 (s, 9H), 1.21 (s, 9H), 1.21 (d, J=6.6 Hz, 3H, H-6); 13C NMR (CDCl3, 68 MHz) δ 177.2, 177.4, 177.1, 133.5, 131.1, 128.6, 128.4, 128.1, 127.7, 85.1, 73.3, 72.6, 69.9, 66.3, 38.9, 38.6, 26.9, 27.0, 16.4; FABMS C27H39O7S (MNa+) calcd 531.2392, found 531.2404.

Workup

  1. temperaturecooled
  2. washwashed with H2O (100 mL) and saturated NaCl (100 mL)
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-971feffa3a5d497fa756abde85f6ac2d
Source dataset
uspto-grants-2000_03
Patent number
US06040433

Reaction notes

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