Trimethylsilyl triflate → HCID 86584852, compound

HRID 458343Notes

Reaction equation

HRID 458343 reaction equation
[OH:1][CH2:2][C@H:3]1[N:7]([S:8]([CH3:11])(=[O:10])=[O:9])[CH2:6][C@H:5]([S:12][C:13](=[O:15])[CH3:14])[CH2:4]1.C(O[C@H:20]1[O:37][C@@H:36]([CH3:38])[C@H:31]([O:32][C:33](=[O:35])[CH3:34])[C@@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]1[O:22][C:23](=[O:25])[CH3:24])(=O)C.FC(F)(F)S(O[Si](C)(C)C)(=O)=O.C(=O)(O)[O-].[Na+]>ClCCl>[C:28]([O:27][C@@H:26]1[C@@H:31]([O:32][C:33](=[O:35])[CH3:34])[C@H:36]([CH3:38])[O:37][C@H:20]([O:1][CH2:2][C@@H:3]2[CH2:4][C@@H:5]([S:12][C:13](=[O:15])[CH3:14])[CH2:6][N:7]2[S:8]([CH3:11])(=[O:10])=[O:9])[C@@H:21]1[O:22][C:23](=[O:25])[CH3:24])(=[O:30])[CH3:29]

Participants

6

Reactant 4

HCID 65367Trimethylsilyl triflateHCID 516892Sodium BicarbonateHCID 11012994HCID 11012994, compoundHCID 86584850HCID 86584850, compound

Product 1

HCID 86584852HCID 86584852, compoundYield 72.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of thioacetic acid (3R,5S)-S-(5-hydroxymethyl-1-methanesulfonyl-pyrrolidin-3-yl) ester (0.070 g) and 1,2,3,4-tetra-O-acetyl-6-deoxy-beta-L-mannopyranose [G. Hodosi and P. Kovàc, Carbohydr. Res., 303, 239–243 (1997)] (0.138 g) in dichloromethane (10.0 ml) was treated with trimethylsilyl trifluoromethanesulphonate (0.075 ml) at 0° C. The reaction mixture was stirred at 0° C. for 1 h, poured into a sodium bicarbonate solution, and extracted with EtOAc. The organic phase was washed with brine, dried over magnesium sulphate and concentrated. The residue was chromatographed on silica gel using EtOAc/hexane 1:1 as eluent to obtain acetic acid (2S,3R,4R,5S,6S)-4,5-diacetoxy-2-[(2S,4R)-4-acetylsulfanyl-1-methanesulfonyl-pyrrolidin-2-ylmethoxy]-6-methyl-tetrahydro-pyran-3-yl ester (0.105 g) as a syrup, MS: 543 (M+NH4+). Acetic acid (2S,3R,4R,5S,6S)-4,5-diacetoxy-2-[(2S,4R)-4-acetylsulfanyl-1-methanesulfonyl-pyrrolidin-2-ylmethoxy]-6-methyl-tetrahydro-pyran-3-yl ester (0.080 g) was reacted as described for the S-Acetyl deprotection (see below) to obtain (2S,3R,4R,5R,6S)-2-[(2S,4R)-4-mercapto-1-methanesulfonyl-pyrrolidin-2-ylmethoxy]-6-methyl-tetrahydro-pyran-3,4,5-triol (0.035 g) as a colourless foam, MS: 358 (MH+).

Workup

  1. extractionextracted with EtOAc
  2. washThe organic phase was washed with brine
  3. dry with materialdried over magnesium sulphate
  4. concentrationconcentrated
  5. customThe residue was chromatographed on silica gel

Sources & evidence

ORD record
ord-19f36e44306741beb7e472e1df5bd455
Source dataset
uspto-grants-2007_03
Patent number
US07189756B2

Reaction notes

Loading…