Perchloric Acid → 3-((tert-Butyldiphenylsilyl)oxy)cyclobutanone

HRID 717865Notes

Reaction equation

HRID 717865 reaction equation
[C:1]([Si:5]([O:18][CH:19]1[CH2:22][C:21](S(C)=O)(SC)[CH2:20]1)([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)([CH3:4])([CH3:3])[CH3:2].Cl(O)(=O)(=O)=[O:29]>CCOCC.O>[Si:5]([O:18][CH:19]1[CH2:22][C:21](=[O:29])[CH2:20]1)([C:1]([CH3:3])([CH3:4])[CH3:2])([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

5

Reactant 2

HCID 24247Perchloric AcidHCID 86666495Tert-butyl{[3-(methylsulfinyl)-3-(methylthio)cyclobutyl]oxy}diphenylsilane

Product 1

HCID 668245053-((tert-Butyldiphenylsilyl)oxy)cyclobutanoneYield 59%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent

Procedure

A solution of tert-butyl {[3-(methylsulfinyl)-3-(methylthio)cyclobutyl]oxy}diphenylsilane (17.05 g, 40.7 mmol, from Step 2) in ether (350 mL) cooled to 0° C. was treated with a solution of 6 M perchloric acid in water (10 mL) that was pre-diluted with water (7 mL). The bath was removed and stirred overnight. The mixture was poured into pH 7 buffer, and the product was extracted with diethyl ether. The combined extracts were dried over sodium sulfate, decanted and concentrated. The reaction was performed again on the same scale and the two batches were combined for purification. Flash chromatography, eluting with a gradient from 0-5% ethyl acetate/hexanes afforded desired product (15.7 g, 59%). 1H NMR (300 MHz, CDCl3): δ 7.75-7.62 (m, 4H), 7.49-7.33 (m, 6H), 4.59 (tt, 1H), 3.22-3.03 (m, 4H), 1.07 (s, 9H).

Workup

  1. customThe bath was removed
  2. additionThe mixture was poured into pH 7 buffer
  3. extractionthe product was extracted with diethyl ether
  4. dry with materialThe combined extracts were dried over sodium sulfate
  5. customdecanted
  6. concentrationconcentrated
  7. customthe two batches were combined for purification
  8. washFlash chromatography, eluting with a gradient from 0-5% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-e9eea22c45ae487ebb3b1daeed44ca54
Source dataset
uspto-grants-2015_11
Patent number
US09193733B2

Reaction notes

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