Triphenylphosphine → (2S,5R)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-3-(2-((tert-butyldimethylsilyl)oxy)ethyl)-2-(((tert-butyldimethylsilyl)oxy)methyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 627285Notes

Reaction equation

HRID 627285 reaction equation
OC1CN(C([O-])=O)CC=C1.[Si:11]([O:18][CH2:19][CH2:20][C:21]1[C@@H:22]([CH2:35][O:36][Si:37]([C:40]([CH3:43])([CH3:42])[CH3:41])([CH3:39])[CH3:38])[N:23]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:24][C@@H:25](O)[CH:26]=1)([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:63]([O:66][NH:67][S:68]([C:71]1[CH:76]=[CH:75][CH:74]=[CH:73][C:72]=1[N+:77]([O-:79])=[O:78])(=[O:70])=[O:69])[CH:64]=[CH2:65].N(C(OC(C)C)=O)=NC(OC(C)C)=O>C1(C)C=CC=CC=1>[CH2:63]([O:66][N:67]([C@H:25]1[CH2:24][N:23]([C:28]([O:30][C:31]([CH3:33])([CH3:32])[CH3:34])=[O:29])[C@H:22]([CH2:35][O:36][Si:37]([C:40]([CH3:41])([CH3:43])[CH3:42])([CH3:39])[CH3:38])[C:21]([CH2:20][CH2:19][O:18][Si:11]([C:14]([CH3:15])([CH3:16])[CH3:17])([CH3:12])[CH3:13])=[CH:26]1)[S:68]([C:71]1[CH:76]=[CH:75][CH:74]=[CH:73][C:72]=1[N+:77]([O-:79])=[O:78])(=[O:70])=[O:69])[CH:64]=[CH2:65]

Participants

7

Reactant 5

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 154979112-Nitro-N-[(prop-2-en-1-yl)oxy]benzene-1-sulfonamideHCID 218741495-hydroxy-5,6-dihydropyridine-1(2H)-carboxylateHCID 89852358(2S,5S)-tert-butyl 3-(2-((tert-butyldimethylsilyl)oxy)ethyl)-2-(((tert-butyldimethylsilyl)oxy)methyl)-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate

Product 1

HCID 131735303(2S,5R)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-3-(2-((tert-butyldimethylsilyl)oxy)ethyl)-2-(((tert-butyldimethylsilyl)oxy)methyl)-5,6-dihydropyridine-1(2H)-carboxylateYield 69.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of (2S,5S)-tert-butyl 3-(2-((tert-butyldimethylsilyl)oxy)ethyl)-2-((tert-butyldimethylsilyl)oxy)methyl)-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 281, 7.33 g, 14.61 mmol) in toluene (100 mL) at room temperature was added triphenylphosphine (4.58 g, 17.53 mmol), N-(allyloxy)-2-nitrobenzenesulfonamide (3.77 g, 14.61 mmol) and diisopropyl azodicarboxylate (3.45 mL, 17.53 mmol). The reaction mixture was stirred overnight at room temperature then concentrated. The resulting oil was triturated with hexane and filtered to remove triphenylphosphine oxide. The filtrate was concentrated onto silica gel. Silica gel chromatography (0%-20% ethyl acetate/hexanes) afforded the title compound (7.5 g, 69.2%) as a light yellow oil.

Workup

  1. concentrationthen concentrated
  2. customThe resulting oil was triturated with hexane
  3. filtrationfiltered
  4. customto remove triphenylphosphine oxide
  5. concentrationThe filtrate was concentrated onto silica gel

Sources & evidence

ORD record
ord-0152ac7abb524fe2a19596dee5b12c2c
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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