Methanesulfonic Acid → HCID 59557745, compound

HRID 425087Notes

Reaction equation

HRID 425087 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Cl:8])=[C:4]([CH2:9][C:10]2[CH:15]=[CH:14][C:13]([CH2:16][CH2:17][O:18][CH:19]3[CH2:21][CH2:20]3)=[CH:12][CH:11]=2)[CH:3]=1.[Li][CH2:23]CCC.C[Si](C)(C)[O:29][C@@H:30]1[C@@H:35]([O:36][Si](C)(C)C)[C@H:34]([O:41][Si](C)(C)C)[C@@H:33]([CH2:46][O:47][Si](C)(C)C)[O:32][C:31]1=[O:52].CS(O)(=O)=O>C1(C)C=CC=CC=1.C1COCC1.C1(C)C=CC=CC=1.CO>[Cl:8][C:5]1[CH:6]=[CH:7][C:2]([C:31]2([O:52][CH3:23])[C@H:30]([OH:29])[C@@H:35]([OH:36])[C@H:34]([OH:41])[C@@H:33]([CH2:46][OH:47])[O:32]2)=[CH:3][C:4]=1[CH2:9][C:10]1[CH:15]=[CH:14][C:13]([CH2:16][CH2:17][O:18][CH:19]2[CH2:21][CH2:20]2)=[CH:12][CH:11]=1

Participants

8

Reactant 4

HCID 6395Methanesulfonic AcidHCID 10994280(3R,4S,5R,6R)-3,4,5-Tris-trimethylsilanyloxy-6-trimethylsilanyloxymethyl-tetrahydro-pyran-2-onHCID 59557748HCID 59557748, compoundHCID 178418339Butyllithium

Product 1

HCID 59557745HCID 59557745, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 1140TolueneSolventHCID 22635083Tetrahydrofuran tolueneSolvent

Conditions

Temperature
-65 °C

Procedure

To a solution of 4-bromo-1-chloro-2-(4-(2-cyclopropoxyethyl)benzyl)benzene (105 mg, 0.29 mmol) in anhydrous toluene/THF (1.2 mL, v/v=2:1) was added dropwise n-BuLi (2.5 M in hexane, 0.14 mL) at −65° C., and the mixture was stirred for 30 min at −65° C. Then a −65° C. solution of (3R,4S,5R,6R)-3,4,5-tris(trimethylsilyloxy)-6-((trimethylsilyloxy)methyl)tetrahydro-2H-pyran-2-one (148 mg, 0.32 mmol) in toluene (1.2 mL) was added dropwise over 15 min. The mixture was stirred at −65° C. for 3 h until starting material was consumed. The reaction was quenched with methanesulfonic acid (0.04 mL, 0.60 mmol) in methanol (1 mL), and the mixture was allowed to warm to room temperature and stirred overnight. The reaction was quenched with saturated sodium bicarbonate, the organic phase was separated and the aqueous phase was extracted with ethyl acetate. The combined organic phases were washed with saturated bicarbonate, then with water, and then with brine, and dried over sodium sulfate. Removal of the volatiles afforded a residue (134 mg), which was used in the next step without further purification.

Workup

  1. stirringThe mixture was stirred at −65° C. for 3 h
  2. customwas consumed
  3. temperatureto warm to room temperature
  4. stirringstirred overnight
  5. customThe reaction was quenched with saturated sodium bicarbonate
  6. customthe organic phase was separated
  7. extractionthe aqueous phase was extracted with ethyl acetate
  8. washThe combined organic phases were washed with saturated bicarbonate
  9. dry with materialwith water, and then with brine, and dried over sodium sulfate
  10. customRemoval of the volatiles

Sources & evidence

ORD record
ord-3bc3d629ed244b0486a6d3b3c826cdc8
Source dataset
uspto-grants-2012_01
Patent number
US08106021B2

Reaction notes

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