Triphenylphosphine → HCID 118079228, compound

HRID 1485678Notes

Reaction equation

HRID 1485678 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([NH:13][S:14]([C:17]2[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][CH:18]=2)(=[O:16])=[O:15])[C:5]([NH:8][C@@H:9]([CH3:12])[CH2:10]O)=[N:6][CH:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C1COCC1>[Br:1][C:2]1[CH:7]=[N:6][C:5]2[NH:8][C@@H:9]([CH3:12])[CH2:10][N:13]([S:14]([C:17]3[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][CH:18]=3)(=[O:16])=[O:15])[C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 118079739HCID 118079739, compound

Product 1

HCID 118079228HCID 118079228, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of (S)-N-(5-bromo-2-(1-hydroxypropan-2-ylamino)pyridin-3-yl)-4-methylbenzenesulfonamide (6.39 g, 15.96 mmol) and triphenylphosphine (5.02 g, 19.16 mmol) in THF (160 ml) was heated to 60° C. whereupon diisopropyl azodicarboxylate (3.72 mL, 19.16 mmol) was added dropwise to the warm solution over a 5 minute period. Heating was discontinued after 5 minutes, and after cooling briefly, the solution was concentrated under reduced pressure. The residue was dissolved in dichloromethane and purified by column chromatography on silica gel (eluting with 6:1 dichloromethane-ethyl acetate followed by 5:1 dichloromethane-ethyl acetate) to afford (S)-7-bromo-3-methyl-1-tosyl-1,2,3,4-tetrahydropyrido[3,2-b]pyrazine a tan, waxy solid (3.12 g) which was used without further purification. MS (ESI, pos. ion) m/z 382, 384 [M+1]+.

Workup

  1. additionwas added dropwise to the warm solution over a 5 minute period
  2. temperatureHeating
  3. temperatureafter cooling briefly
  4. concentrationthe solution was concentrated under reduced pressure
  5. dissolutionThe residue was dissolved in dichloromethane
  6. custompurified by column chromatography on silica gel (eluting with 6:1 dichloromethane-ethyl acetate followed by 5:1 dichloromethane-ethyl acetate)

Sources & evidence

ORD record
ord-8f6e00fcb1c144a191cab5f508392c4c
Source dataset
uspto-grants-2016_08
Patent number
US09422281B2

Reaction notes

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