Hydrochloric Acid → HCID 86760381, compound

HRID 348244Notes

Reaction equation

HRID 348244 reaction equation
[O:1]=[C:2]([C@H:23]([CH3:70])[C@@H:24]([O:61][C:62]([O:64][CH2:65][C:66]([Cl:69])([Cl:68])[Cl:67])=[O:63])[C@@H:25]([CH3:60])[CH2:26]/[CH:27]=[CH:28]/[C:29](/[CH3:59])=[CH:30]\[CH2:31][C@H:32]([O:51][Si](CC)(CC)CC)/[C:33](/[CH3:50])=[CH:34]/[C:35]1[N:36]=[C:37]([CH2:40][O:41][C:42]([O:44][CH2:45][C:46]([Cl:49])([Cl:48])[Cl:47])=[O:43])[S:38][CH:39]=1)[C:3]([CH3:22])([CH3:21])[C@@H:4]([O:13][Si:14]([CH2:19][CH3:20])([CH2:17][CH3:18])[CH2:15][CH3:16])[CH2:5][C:6]([O:8]C(C)(C)C)=[O:7].N1C(C)=CC=CC=1C.FC(F)(F)S(O[Si](CC)(CC)CC)(=O)=O.Cl.P([O-])([O-])([O-])=O>C(Cl)Cl.C(OCC)(=O)C>[O:1]=[C:2]([C@H:23]([CH3:70])[C@@H:24]([O:61][C:62]([O:64][CH2:65][C:66]([Cl:67])([Cl:68])[Cl:69])=[O:63])[C@@H:25]([CH3:60])[CH2:26]/[CH:27]=[CH:28]/[C:29](/[CH3:59])=[CH:30]\[CH2:31][C@H:32]([OH:51])/[C:33](/[CH3:50])=[CH:34]/[C:35]1[N:36]=[C:37]([CH2:40][O:41][C:42]([O:44][CH2:45][C:46]([Cl:47])([Cl:48])[Cl:49])=[O:43])[S:38][CH:39]=1)[C:3]([CH3:22])([CH3:21])[C@@H:4]([O:13][Si:14]([CH2:19][CH3:20])([CH2:15][CH3:16])[CH2:17][CH3:18])[CH2:5][C:6]([OH:8])=[O:7]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 1061PhosphateHCID 79372,6-LutidineHCID 2733308Triethylsilyl trifluoromethanesulphonateHCID 86760382HCID 86760382, compound

Product 1

HCID 86760381HCID 86760381, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of tert-butyl (3S,6R,7S,8S,10E,12Z,15S,16E)-5-oxo-3,15-bis(triethylsilyloxy)-17-(2-(2,2,2-trichloroethoxycarbonyloxymethyl)thiazol-4-yl)-4,4,6,8,12,16-hexamethyl-7-(2,2,2-trichloroethoxycarbonyloxy)-heptadeca-10,12,16-trienoate (2.8 g) in 12 mL of CH2Cl2 is treated with 2,6-lutidine (0.86 mL) and triethylsilyl trifluoromethanesulfonate (0.98 g) at 0° C. for 30 minutes, then at ambient temperature for 10 hours. The mixture is diluted with 50 mL of ethyl acetate and poured into 20 mL of 1 N HCl. The organic phase is separated, washed with pH 7 phosphate buffer, dried with Na2SO4, filtered, and concentrated. The residue is dissolved in 5 mL of THF and treated with 0.5 mL of 0.1 N HCl in methanol. The reaction is monitored by thin-layer chromatography, with additional aliquots of methanolic HCl being added to achieve complete reaction. When complete, the reaction is poured into 15 mL of pH 7 phosphate buffer and extracted with ethyl acetate. The extract is washed with brine, dried with Na2SO4, filtered, and evaporated. The product is purified by flash chromatography on SiO2 (1:1 hexanes/ethyl acetate).

Workup

  1. customThe organic phase is separated
  2. washwashed with pH 7 phosphate buffer
  3. dry with materialdried with Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. dissolutionThe residue is dissolved in 5 mL of THF
  7. additiontreated with 0.5 mL of 0.1 N HCl in methanol
  8. additionadded
  9. customreaction
  10. extractionextracted with ethyl acetate
  11. washThe extract is washed with brine
  12. dry with materialdried with Na2SO4
  13. filtrationfiltered
  14. customevaporated
  15. customThe product is purified by flash chromatography on SiO2 (1:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-019b5482430d43ca81fb5ae48bade5d0
Source dataset
uspto-grants-2007_02
Patent number
US07176235B2

Reaction notes

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