Triphenylphosphine → (2S,5R)-tert-butyl 5-(N-(allyloxy)-2,4-dinitrophenylsulfonamido)-2-((tert-butyldimethylsilyloxy)methyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 627156Notes

Reaction equation

HRID 627156 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]1[CH:15]=[CH:14][C@H:13](O)[CH2:12][N:11]1[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[CH2:43]([O:46][NH:47][S:48]([C:51]1[CH:56]=[CH:55][C:54]([N+:57]([O-:59])=[O:58])=[CH:53][C:52]=1[N+:60]([O-:62])=[O:61])(=[O:50])=[O:49])[CH:44]=[CH2:45].N(C(OC(C)C)=O)=NC(OC(C)C)=O>C1(C)C=CC=CC=1>[CH2:43]([O:46][N:47]([C@H:13]1[CH2:12][N:11]([C:17]([O:19][C:20]([CH3:21])([CH3:23])[CH3:22])=[O:18])[C@H:10]([CH2:9][O:8][Si:1]([C:4]([CH3:6])([CH3:5])[CH3:7])([CH3:3])[CH3:2])[CH:15]=[CH:14]1)[S:48]([C:51]1[CH:56]=[CH:55][C:54]([N+:57]([O-:59])=[O:58])=[CH:53][C:52]=1[N+:60]([O-:62])=[O:61])(=[O:50])=[O:49])[CH:44]=[CH2:45]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 89851401N-(allyloxy)-2,4-dinitrobenzenesulfonamideHCID 89852438(2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 89852173(2S,5R)-tert-butyl 5-(N-(allyloxy)-2,4-dinitrophenylsulfonamido)-2-((tert-butyldimethylsilyloxy)methyl)-5,6-dihydropyridine-1(2H)-carboxylateYield 96.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a stirred solution of (2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 125, 17.50 g, 50.94 mmol), phosphorus triphenyl (14.70 g, 56.04 mmol), N-(allyloxy)-2,4-dinitrobenzenesulfonamide (16.22 g, 53.49 mmol) in toluene (380 mL) was added diisopropyl azodicarboxylate (11.03 ml, 56.04 mmol) at room temperature. The reaction mixture was stirred at rt overnight. The mixture was concentrated and the residue was purified by silica gel column (220 g, 0-40% Hex/EA) to give the desired product (30.8 g) as a yellow gum.

Workup

  1. concentrationThe mixture was concentrated
  2. customthe residue was purified by silica gel column (220 g, 0-40% Hex/EA)

Sources & evidence

ORD record
ord-696645bc335f444caf17401c26cc0f68
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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