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

HRID 627221Notes

Reaction equation

HRID 627221 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]1[C:15]([CH2:16][CH3:17])=[CH:14][C@H:13](O)[CH2:12][N:11]1[C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH2:26]([O:29][NH:30][S:31]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=1[N+:40]([O-:42])=[O:41])(=[O:33])=[O:32])[CH:27]=[CH2:28].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>[CH2:26]([O:29][N:30]([C@H:13]1[CH2:12][N:11]([C:19]([O:21][C:22]([CH3:23])([CH3:25])[CH3:24])=[O:20])[C@H:10]([CH2:9][O:8][Si:1]([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:2])[CH3:3])[C:15]([CH2:16][CH3:17])=[CH:14]1)[S:31]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=1[N+:40]([O-:42])=[O:41])(=[O:33])=[O:32])[CH:27]=[CH2:28]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 154979112-Nitro-N-[(prop-2-en-1-yl)oxy]benzene-1-sulfonamide2×HCID 89852682(2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-3-ethyl-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 89852449(2S,5R)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-2-((tert-butyldimethylsilyloxy)methyl)-3-ethyl-5,6-dihydropyridine-1(2H)-carboxylateYield 66.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a stirred suspension of (2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-3-ethyl-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 208, 6.36 g, 17.12 mmol), N-(allyloxy)-2-nitrobenzenesulfonamide (Intermediate 9) (8.84 g, 34.23 mmol) and triphenylphosphine (13.47 g, 51.35 mmol) in toluene (25 mL) at 0° C. was added dropwise (E)-diisopropyl diazene-1,2-dicarboxylate (9.95 ml, 51.35 mmol). The reaction mixture was warmed to room temperature and stirred for 30 minutes. Silica gel chromatography (0-40% ethyl acetate/hexanes) afforded the title compound (7.00 g, 66.8%) as a yellow oil.

Sources & evidence

ORD record
ord-98969bf7dad74e34872c509fe71417f2
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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