Dimethyl Sulfoxide → (S,4E)-3-(tert-Butyldimethylsilyloxy)-4-methyl-5-(2-methyl-thiazol-4-yl)-pent-4-enal

HRID 1700960Notes

Reaction equation

HRID 1700960 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[Si:11]([O:18][C@H:19](/[C:23](/[CH3:31])=[CH:24]/[C:25]1[N:26]=[C:27]([CH3:30])[S:28][CH:29]=1)[CH2:20][CH2:21][OH:22])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12].C(N(CC)CC)C>ClCCl.O>[Si:11]([O:18][C@H:19](/[C:23](/[CH3:31])=[CH:24]/[C:25]1[N:26]=[C:27]([CH3:30])[S:28][CH:29]=1)[CH2:20][CH:21]=[O:22])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:12])[CH3:13]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 10936330(-)-(3S,4E)-3-{[tert-Butyl(dimethyl)silyl]oxy}-4-methyl-5-(2-methyl-1,3-thiazol-4-yl)pent-4-en-1-ol

Product 1

HCID 11045612(S,4E)-3-(tert-Butyldimethylsilyloxy)-4-methyl-5-(2-methyl-thiazol-4-yl)-pent-4-enalYield 82.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-78 °C

Procedure

A solution of dimethyl sulfoxide (2,04 ml, 28.8 mmol, 2.4 equiv) in 6.0 ml of dichloromethane is added dropwise within 5 min to a stirred solution of oxalyl chloride (1.14 ml, 13.2 mmol, 1.1 equiv) in 30 ml of dichloromethane cooled to −78° C. The mixture is stirred for 10 min at −70° C. A solution of (S,4E)-3-(tert-butyldimethylsilyloxy)-1-hydroxy-4-methyl-5-(2-methylthiazol-4-yl)-pent-4-ene 16 (3.93 g, 12.0 mmol) in 5 ml of dichloromethane is added dropwise within 5 min. The mixture is stirred for 30 min at −70° C. The reaction is quenched by dropwise addition of triethyl amine (8.4 ml, 60.0 mmol). The mixture is warmed to r.t. within 45 min. Water (30 ml) is added and the mixture is stirred for 10 min. The organic layer is seperated and the aqueous layer is extracted with dichloromethane (3×100 ml). The combined organic extracts are dried over magnesium sulfate and concentrated in vacuo. Purification of the residue by flash column chromatography (pentane/diethyl ether 5:2) affords (S,4E)-3-(tert-butyadimethylsilyloxy)-4-methyl-5-(2-methylthiazol-4-yl)-pent-4en-1-al 17 (3.21 g, 82%) as a pale yellow oil.

Workup

  1. stirringThe mixture is stirred for 30 min at −70° C
  2. temperatureThe mixture is warmed to r.t. within 45 min
  3. stirringthe mixture is stirred for 10 min
  4. customThe organic layer is seperated
  5. extractionthe aqueous layer is extracted with dichloromethane (3×100 ml)
  6. dry with materialThe combined organic extracts are dried over magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. customPurification of the residue by flash column chromatography (pentane/diethyl ether 5:2)

Sources & evidence

ORD record
ord-0b1aecd625f3441f91906c3800560430
Source dataset
uspto-grants-2002_02
Patent number
US06350878B1

Reaction notes

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