(6S)-tert-butyl 6-((tert-butyldimethylsilyloxy)methyl)-5-methyl-3-(trimethylsilyloxy)-5,6-dihydropyridine-1(2H)-carboxylate → (S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-3-methyl-5-oxo-5,6-dihydropyridine-1 (2H)-carboxylate

HRID 627124Notes

Reaction equation

HRID 627124 reaction equation
[Si:1]([O:8][CH2:9][C@H:10]1[N:15]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:14][C:13]([O:23][Si](C)(C)C)=[CH:12][CH:11]1[CH3:28])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]>C(#N)C.CCOC(C)=O.CC([O-])=O.CC([O-])=O.[Pd+2]>[Si:1]([O:8][CH2:9][C@@H:10]1[C:11]([CH3:28])=[CH:12][C:13](=[O:23])[CH2:14][N:15]1[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])([C:4]([CH3:7])([CH3:5])[CH3:6])([CH3:3])[CH3:2]

Participants

5

Reactant 1

HCID 89852093(6S)-tert-butyl 6-((tert-butyldimethylsilyloxy)methyl)-5-methyl-3-(trimethylsilyloxy)-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 89852188(S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-3-methyl-5-oxo-5,6-dihydropyridine-1 (2H)-carboxylateYield 58.3%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

The crude (6S)-tert-butyl 6-((tert-butyldimethylsilyloxy)methyl)-5-methyl-3-(trimethylsilyloxy)-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 77, 12.58 g, 29.27 mmol) in 8 mL ACN was stirred at rt with Pd(OAc)2 (6.57 g, 29.27 mmol) for 2 days. The mixture was diluted with 160 mL EtOAc, filtered through celite, concentrated in vacuo and subjected to flash chromatography (220 g, 0-30% EA/Hex) to obtain the desired product (6.07 g, 58.3%) (over two steps) as a beige solid.

Workup

  1. filtrationfiltered through celite
  2. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-80643f3e29c24c4fa91fd4f8c75e8477
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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