Dimethyl Sulfoxide → tert-Butyl 4-formyl-4-(2-(tert-butyldimethylsilyloxy)eth-1-yl)piperidine-1-carboxylate

HRID 8768Notes

Reaction equation

HRID 8768 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[OH:11][CH2:12][C:13]1([CH2:26][CH2:27][O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30])[CH2:18][CH2:17][N:16]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:15][CH2:14]1.C(N(CC)CC)C>C(Cl)Cl.O>[CH:12]([C:13]1([CH2:26][CH2:27][O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:30])[CH3:31])[CH2:14][CH2:15][N:16]([C:19]([O:21][C:22]([CH3:24])([CH3:25])[CH3:23])=[O:20])[CH2:17][CH2:18]1)=[O:11]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 21983900tert-Butyl 4-hydroxymethyl-4-(2-(tert-butyldimethylsilyloxy)eth-1-yl)piperidine-1-carboxylate

Product 1

HCID 21983955tert-Butyl 4-formyl-4-(2-(tert-butyldimethylsilyloxy)eth-1-yl)piperidine-1-carboxylateYield 89.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of oxalyl chloride (3.3 mL, 38 mmol) in methylene chloride (500 mL) at −70° C. was added DMSO (5.4 mL, 76 mmol) over 5 min. After 15 min, a solution of tert-butyl 4-hydroxymethyl-4-(2-(tert-butyldimethylsilyloxy)eth-1-yl)piperidine-1-carboxylate (7.1 g, 19 mmol) in methylene chloride (125 mL) was slowly added over 15 min. After 1 h, triethylamine (21.2 mL, 152 mmol) was added and the reaction was allowed to warm to room temperature for 1 h. The mixture was poured into water and extracted three times with methylene chloride. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated. The residue was purified by flash chromatography (40% ethyl acetate in hexanes) to afford the title product (6.3 g).

Workup

  1. waitAfter 1 h
  2. extractionextracted three times with methylene chloride
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography (40% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-4bd35abee2ce4dad988436debf719e15
Source dataset
uspto-grants-2006_08
Patent number
US07091211B2

Reaction notes

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