Sodium Hydroxide → Castanospermine

HRID 2371569Notes

Reaction equation

HRID 2371569 reaction equation
[OH:1][CH:2]1[CH:9]2[CH:5](OC(C)(C)[O:8]2)[O:4][CH:3]1[CH:12]1[CH:16]([OH:17])[CH2:15][CH2:14][NH:13]1.[OH-].[Na+]>O.[Pt]>[CH2:15]1[C@H:16]([OH:17])[C@H:12]2[N:13]([CH2:5][C@H:9]([OH:8])[C@@H:2]([OH:1])[C@@H:3]2[OH:4])[CH2:14]1

Participants

5

Reactant 2

HCID 14798Sodium HydroxideHCID 147293412-(Tetrahydro-6-hydroxy-2,2dimethylfuro[2,3-d]-l,3-dioxol-5-yl)-3-pyrrolidinol

Product 1

HCID 54445Castanospermine

Reagents, catalysts & solvents 2

HCID 23939PlatinumCatalystHCID 962WaterSolvent

Procedure

A solution of [3aR-[3aα,5α(2R*,3S*),6α,6aα]]-2-(Tetrahydro-6-hydroxy-2,2-dimethylfuro[2,3-d]-1,3-dioxol-5-yl)-3-pyrrolidinol (V) (0.5 g, 2.0 mmol) in trifluoroacetic-water (9:1) (25 mL) was stirred, under nitrogen, at ambient temperature for 20 h. The purple solution was then concentrated in vacuo (40° C.) leaving a thick syrup which was dissolved in deionized water (25 mL). This solution was basified to a pH of about 9.0 by the addition of 1N aqueous sodium hydroxide (5.5 mL) and hydrogenated at 3.4 atmospheres over 5% Pt on carbon (0.3 g) on a Parr apparatus for 16 h. The mixture was filtered through a celite pad and the collected catalyst washed with water (2×20 mL). The combined filtrate was adsorbed on a column of Dowex 50 W-X8 (H+) ion exchange resin (10 mL) (prewashed with 200 mL of water) and eluted first with deionized water (200 mL) and then with 1N ammonium hydroxide solution (twenty×20 mL fractions were collected). (+)-Castanospermine (VI), 0.23 g (61%) was obtained from fractions 1-15. An analytical sample was obtained as colorless prisms by recrystallization from 90% ethanol: mp 210°-212° C. dec. [lit. 212°-215° C. dec]; [α]D25 =81.4° (c 1.0, H2O) [lit. [α]D25 =+79.7° (C 0.93, H2O)]; 1H NMR (D2O) δ 4.42 (ddd, 1, J=7.0, 4.5, 2.1Hz, H-1), 3.62 (ddd, 1, J=10.6, 9.4, 5.1 Hz, H-6), 3.60 (dd, 1, J=9.8, 9.0 Hz, H-8), 3.32 (dd, 1, J=9.8, 9.0 Hz, H-7) 3.18 (dd, 1, J=10.8, 5.1 Hz, H-5), 3.08 (ddd, 1, J=9.0, 8.8, 8.8 Hz, H-3), 2.34 (dddd, 1, J=13.9, 9.0, 7.0, 2.2 Hz, H-2), 2.22 (ddd, 1, J=9.3, 9.0, 8.8 Hz, H-3'), 2.06 (dd, 1, J=10.8, 10.6 Hz, H-5'), 2.02 (dd, 1, J=9.8, 4.5Hz, H-8a), 1.71(dddd, 1, J=13.9, 9.3, 8.8, 2.1 Hz, H-2'); 13C NMR (D2O) δ 35.6, 54.5, 58.3, 71.9, 72.5, 73.0, 74.3, 81.9; mass spectrum, m/z(rel intensity) 190 (MH+, 50), 172 (MH+ -H2O, 100).

Workup

  1. concentrationThe purple solution was then concentrated in vacuo (40° C.)
  2. customleaving a thick syrup which
  3. filtrationThe mixture was filtered through a celite pad
  4. washthe collected catalyst washed with water (2×20 mL)
  5. washeluted first with deionized water (200 mL)

Sources & evidence

ORD record
ord-18a001cddfd944e7b0a46b4fb68cf733
Source dataset
uspto-grants-1992_03
Patent number
US05093501

Reaction notes

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