Triphenylphosphine → (2S,5R)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-2-((tert-butyldimethyl-silyloxy)methyl)-4-(dimethylcarbamoyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 627165Notes

Reaction equation

HRID 627165 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]1[CH:15]=[C:14]([C:16](=[O:20])[N:17]([CH3:19])[CH3:18])[C@H:13](O)[CH2:12][N:11]1[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH2:29]([O:32][NH:33][S:34]([C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][C:38]=1[N+:43]([O-:45])=[O:44])(=[O:36])=[O:35])[CH:30]=[CH2:31].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(/C(OC(C)C)=O)=N\C(OC(C)C)=O>C1(C)C=CC=CC=1>[CH2:29]([O:32][N:33]([C@H:13]1[CH2:12][N:11]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C@H:10]([CH2:9][O:8][Si:1]([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:3])[CH3:2])[CH:15]=[C:14]1[C:16](=[O:20])[N:17]([CH3:19])[CH3:18])[S:34]([C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][C:38]=1[N+:43]([O-:45])=[O:44])(=[O:36])=[O:35])[CH:30]=[CH2:31]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 154979112-Nitro-N-[(prop-2-en-1-yl)oxy]benzene-1-sulfonamideHCID 89851842(2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-4-(dimethylcarbamoyl)-5-hydroxy-5,6-dihydropyridine-1 (2H)-carboxylate2×

Product 1

HCID 89851804(2S,5R)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-2-((tert-butyldimethyl-silyloxy)methyl)-4-(dimethylcarbamoyl)-5,6-dihydropyridine-1(2H)-carboxylateYield 82%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A stirred suspension of (2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-4-(dimethylcarbamoyl)-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 137, 3.09 g, 7.45 mmol), N-(allyloxy)-2-nitrobenzenesulfonamide (2.348 g, 9.09 mmol) and triphenylphosphine (2.150 g, 8.20 mmol) in toluene (65 mL) was cooled in a salt-ice-bath and then (E)-diisopropyl diazene-1,2-dicarboxylate (1.588 mL, 8.20 mmol) was added dropwise. The reaction was let warm up to rt and was stirred for an additional 2 h. The solvent was removed and the crude product was loaded onto silica gel, purified via flash chromatography (25-75% EA/Hex) to obtain the desired product (4.0 g, 82%) as an off-white solid.

Workup

  1. temperaturewas cooled in a salt-ice-bath
  2. customThe solvent was removed
  3. custompurified via flash chromatography (25-75% EA/Hex)

Sources & evidence

ORD record
ord-7b9ce92918964d3b848a0dd942dc236c
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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