Methanesulfonic Acid → HCID 86729315, compound

HRID 1474601Notes

Reaction equation

HRID 1474601 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([Cl:23])=[C:6]([CH:22]=1)[CH2:7][C:8]1[CH:21]=[CH:20][C:11]([O:12][Si:13]([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14])=[CH:10][CH:9]=1.[Li][C:25](C)(C)C.C[Si](C)(C)[O:31][C@@H:32]1[C@@H:37]([O:38][Si](C)(C)C)[C@H:36]([O:43][Si](C)(C)C)[C@@H:35]([CH2:48][O:49][Si](C)(C)C)[O:34][C:33]1=[O:54].CS(O)(=O)=O>C1COCC1.CO.C(OC(=O)C)C>[Si:13]([O:12][C:11]1[CH:20]=[CH:21][C:8]([CH2:7][C:6]2[CH:22]=[C:2]([C@@:33]3([O:54][CH3:25])[C@H:32]([OH:31])[C@@H:37]([OH:38])[C@H:36]([OH:43])[C@@H:35]([CH2:48][OH:49])[O:34]3)[CH:3]=[CH:4][C:5]=2[Cl:23])=[CH:9][CH:10]=1)([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14]

Participants

8

Reactant 4

HCID 6395Methanesulfonic AcidHCID 10994280(3R,4S,5R,6R)-3,4,5-Tris-trimethylsilanyloxy-6-trimethylsilanyloxymethyl-tetrahydro-pyran-2-onHCID 59747702(4-(5-Bromo-2-chlorobenzyl)phenoxy)(tert-butyl)dimethylsilaneHCID 178418306HCID 178418306, compound

Product 1

HCID 86729315HCID 86729315, compoundYield 55.4%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of (4-(5-bromo-2-chlorobenzyl)phenoxy)(tert-butyl)dimethylsilane (67.0 g, 0.163 mol, prepared by following the procedure given in US20070049537) in dry THF (1.0 L), tBuLi (228 mL, 0.342 mol, 1.6 M solution in pentane) was added at −78° C. The reaction mixture was stirred at the same temperature for 30 mM. A solution of (3R,4S,5R,6R)-3,4,5-tris((trimethylsilyl)oxy)-6-(((trimethylsilyl)oxy)methyl)tetrahydro-2H-pyran-2-one (77.8 g, 0.167 mol, prepared following the procedure given in US20070049537) in dry THF (272 mL) was introduced into it at the same temperature and stirred for another 4 h. A solution of methanesulfonic acid (18.35 mL, 0.283 mol) in methanol (586 mL) was added and the temperature was raised to r.t. gradually and stirred for 16 h. The reaction was quenched by the addition of saturated aqueous solution of NaHCO3 (500 mL) and volatiles were evaporated in vacuo. The residue obtained was dissolved in ethylacetate (1 L), washed with water (500 mL) and brine (500 mL) successively. The organic layer was dried over anhydrous Na2SO4 and volatiles were evaporated in vacuo. The residue obtained was purified by column chromatography (silica gel, 1:9 MeOH:DCM) to provide title compound (47.37 g, 55.4%) as off-white solid.

Workup

  1. additionwas introduced into it at the same temperature
  2. stirringstirred for another 4 h
  3. stirringstirred for 16 h
  4. customThe reaction was quenched by the addition of saturated aqueous solution of NaHCO3 (500 mL) and volatiles
  5. customwere evaporated in vacuo
  6. customThe residue obtained
  7. washwashed with water (500 mL) and brine (500 mL) successively
  8. dry with materialThe organic layer was dried over anhydrous Na2SO4 and volatiles
  9. customwere evaporated in vacuo
  10. customThe residue obtained
  11. customwas purified by column chromatography (silica gel, 1:9 MeOH:DCM)

Sources & evidence

ORD record
ord-98423f269d67414185c3a98300f8282d
Source dataset
uspto-grants-2015_04
Patent number
US09018249B2

Reaction notes

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