Dimethyl Sulfoxide → HCID 59608023, compound

HRID 2191384Notes

Reaction equation

HRID 2191384 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[Cl:11][C:12]1[C:13]([NH:18][CH2:19][C@H:20]([C@H:22]2[C@H:29]3[C@H:25]([O:26][C:27]([CH3:31])([CH3:30])[O:28]3)[CH2:24][CH2:23]2)[OH:21])=[N:14][CH:15]=[CH:16][N:17]=1.C(N(CC)CC)C>C(Cl)Cl>[Cl:11][C:12]1[C:13]([NH:18][CH2:19][C:20]([C@H:22]2[C@H:29]3[C@H:25]([O:26][C:27]([CH3:31])([CH3:30])[O:28]3)[CH2:24][CH2:23]2)=[O:21])=[N:14][CH:15]=[CH:16][N:17]=1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 86648188HCID 86648188, compound

Product 1

HCID 59608023HCID 59608023, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

Oxalyl chloride (2.75 mL, 31.6 mmol, 3.0 equiv) in DCM (35 mL) was added dropwise to DMSO (3.00 mL, 42.1 mmol, 4.0 equiv) in DCM (35 mL) at −78° C. After 30 minutes, (S)-2-(3-chloropyrazin-2-ylamino)-1-((3aS,4S,6aR)-2,2-dimethyltetrahydro-3aH-cyclo-penta[d][1,3]dioxol-4-yl)ethanol (2-7) (3.30 g, 10.5 mmol, 1 equiv) in DCM (35 mL) was added dropwise. The resulting mixture was stirred at −78° C. for 1 hour, at which point triethylamine (6.60 mL, 47.3 mmol, 4.5 equiv) was added. The cooling bath was removed, and after 30 minutes the reaction mixture was concentrated. The resulting yellow residue was purified via flash chromatography on a silica gel column (ethyl acetate/hexanes) to yield 2-(3-chloropyrazin-2-ylamino)-1-((3aS,4R,6aR)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]-dioxol-4-yl)ethanone (2-8) as a yellow solid. 1H NMR (500 MHz, CDCl3): δ 7.92 (d, J=2.7 Hz, 1H); 7.63 (d, J=2.7 Hz, 1H); 5.93 (s, 1H); 4.80 (d, J=5.7 Hz, 1H); 4.73 (t, J=5.4 Hz, 1H); 4.47 (dd, J=19.7, 5.0 Hz, 1H); 4.31 (dd, J=19.7, 4.7 Hz, 1H); 3.17 (d, J=8.1 Hz, 1H); 2.25-2.17 (m, 1H); 1.93-1.84 (m, 2H); 1.78-1.68 (m, 1H); 1.47 (s, 3H); 1.32 (s, 3H). LRMS m/z (M+H) 312.0 found, 312.1 required.

Workup

  1. additionwas added
  2. customThe cooling bath was removed
  3. concentrationafter 30 minutes the reaction mixture was concentrated
  4. customThe resulting yellow residue was purified via flash chromatography on a silica gel column (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-b608714a4e024d2ea7068a325c0481a6
Source dataset
uspto-grants-2012_12
Patent number
US08329697B2

Reaction notes

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