(S,E)-tert-butyl (2,2,3,3,11,11,12,12-octamethyl-7-methylene-4,10-dioxa-3,11-disilatridecan-6-yl)(2-oxopent-3-en-1-yl)carbamate → (S)-tert-butyl 3-(2-((tert-butyldimethylsilyl)oxy)ethyl)-2-(((tert-butyldimethylsilyl)oxy)methyl)-5-oxo-5,6-dihydropyridine-1(2H)-carboxylate

HRID 627283Notes

Reaction equation

[CH3:1][C:2]([CH3:36])([Si:4]([CH3:35])([CH3:34])[O:5][CH2:6][C@@H:7]([N:20]([CH2:28][C:29](=[O:33])/[CH:30]=C/C)[C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[C:8](=C)[CH2:9][CH2:10][O:11][Si:12]([CH3:18])([CH3:17])[C:13]([CH3:16])([CH3:15])[CH3:14])[CH3:3]>C1(C)C=CC=CC=1.CC1C=C(C)C(N2C(=[Ru](Cl)(Cl)=CC3C=CC=CC=3OC(C)C)N(C3C(C)=CC(C)=CC=3C)CC2)=C(C)C=1>[Si:12]([O:11][CH2:10][CH2:9][C:8]1[C@@H:7]([CH2:6][O:5][Si:4]([C:2]([CH3:36])([CH3:3])[CH3:1])([CH3:35])[CH3:34])[N:20]([C:21]([O:22][C:23]([CH3:25])([CH3:24])[CH3:26])=[O:27])[CH2:28][C:29](=[O:33])[CH:30]=1)([C:13]([CH3:15])([CH3:16])[CH3:14])([CH3:18])[CH3:17]

Participants

Conditions

Temperature: 100 °C

Procedure

A solution of (S,E)-tert-butyl (2,2,3,3,11,11,12,12-octamethyl-7-methylene-4,10-dioxa-3,11-disilatridecan-6-yl)(2-oxopent-3-en-1-yl)carbamate (Intermediate 279, 10 g, 18.45 mmol) in toluene (400 mL) was purged with nitrogen for 15 minutes. The Hoveyda-Grubbs Catalyst 2nd Generation (2.320 g, 3.69 mmol) was then added. The reaction was heated at 100° C. overnight. Another 0.05 eq of catalyst was added and the reaction mixture was heated at 100° C. for another 2 hours. The reaction mixture was concentrated onto silica gel. Silica gel chromatography (0%-15% ethyl acetate/hexanes) afforded the title compound (8.55 g, 93%) as a light brown oil.

Workup

temperaturethe reaction mixture was heated at 100° C. for another 2 hours
concentrationThe reaction mixture was concentrated onto silica gel

Sources & evidence

ORD record: ord-19aebe187a6243508cc67fd320cee35f
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09309245B2

Reaction notes

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