Ammonium Chloride → HCID 15119366, compound

HRID 1456835Notes

Reaction equation

HRID 1456835 reaction equation
[CH2:1]1[O:8][C@@H:7]2[O:9][C@H:2]1[C@@H:3]([O:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C@@H:4]1[O:6][C@@H:5]12.[CH:18]([Mg]Br)=[CH2:19].[NH4+].[Cl-]>C1COCC1>[CH2:11]([O:10][C@@H:3]1[C@H:2]2[CH2:1][O:8][C@H:7]([O:9]2)[C@H:5]([CH:18]=[CH2:19])[C@H:4]1[OH:6])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 11031793.beta.-D-Mannopyranose, 1,6:2,3-dianhydro-4-O-(phenylmethyl)-HCID 178418507HCID 178418507, compound

Product 1

HCID 15119366HCID 15119366, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
60 °C

Procedure

To a stirred solution of 1,6:2,3-dianhydro-4-O-benzyl-β-D-mannopyranose (7, 5.0 g, 21.3 mmol) in dry THF (25 ml), was added a solution of 1.77M vinylmagnesiumbromide 16 in THF (120.5 ml, 213 mmol). The mixture was gently refluxed for 3 h at 60° C. After cooling to room temperature a 2M NH4Cl aq. solution (650 ml, pH 8) was slowly added. The aqueous layer was extracted with ethyl acetate (2×250 ml). The combined organic layers were dried (MgSO4), filtered and concentrated. The crude product (4.87 g, 87%) was purified by flash chromatography using ethyl acetate/pentane 1:2 as eluent, to give 1,6-anhydro-4-O-benzyl-2-deoxy-2-C-vinyl-β-D-glucopyranose (8) as a white crystalline compound in 75.5% (4.23 g) yield. After recrystallization in ethanol: mp. 88°-91° C.; [α]D20 =-2.3° (c 4.1, CHCl3) (lit17 mp. 91°-93° C. [α]D20 =+1.2° (c 1.3, CHCl3)). 13C-NMR (50 MHz, CDCl3):δ135.5 (CH=), 137.7, 128.3), 127.6, 127.5 (Ph), 117.2 (CH2 =), 103.5 (C-1), 78.8 (C-4), 74.6 (C-3), 71.3, 70.4 (C-5, OCH2Ph), 65.4 (C-6), 51.8 ppm (C-2). 1H NMR (200 MHz, CDCl3): δ7.35 (d, 5H, Ph), 5.99 (m, 1H, CH=CH2), 5.25 and 5.17 (s, 1H og d, 1H, CH2 =), 4.63) (dd, 3H, OCH2Ph and H-5), 4.09 and 3.75 (d, 1H and m, 2H, H-3, H-6 and H-6'), 3.43 (s, 1H, H-4), 2.80 (broad s, 1H, OH), 2.45 (d, 1H, H-2). Anal. Calc. for C15H18O4 : C, 68.69; H, 6.92. Found: C, 68.58; H, 6.94.

Workup

  1. additionwas slowly added
  2. extractionThe aqueous layer was extracted with ethyl acetate (2×250 ml)
  3. dry with materialThe combined organic layers were dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude product (4.87 g, 87%) was purified by flash chromatography

Sources & evidence

ORD record
ord-ed264c92fe004e3792147b76c59af9a5
Source dataset
uspto-grants-1998_12
Patent number
US05844102

Reaction notes

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