Chlorotrimethylsilane → Benzyl 4-((trimethylsilyl)oxy)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 1926645Notes

Reaction equation

[O:1]=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:9])[CH2:4][CH2:3]1.[CH3:18][Si:19](Cl)([CH3:21])[CH3:20].C(N(CC)CC)C>CN(C=O)C>[CH3:18][Si:19]([CH3:21])([CH3:20])[O:1][C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:9])[CH2:4][CH:3]=1

Participants

Conditions

Temperature: 85 °C

Procedure

To a stirred solution of benzyl 4-oxopiperidine-1-carboxylate (300 g, 1.29 mol) and TMSCl (280 g, 2.58 mol) in DMF (1600 mL) was added triethylamine (457 g, 4.52 mol) at room temperature. After the addition, the reaction mixture was slowly heated to 85° C. and stirred overnight. TLC (EtOAc/Petroleum ether=1:10) showed that the starting material was consumed completely. The reaction mixture was poured into aqueous NaHCO3 (5% w/v) at 0° C. with vigorous stirring and extracted with petroleum ether (3 L, 1 L). The organic layer was dried over sodium sulfate and concentrated to afford benzyl 4-[(trimethylsilyl)oxy]-3,6-dihydropyridine-1(2 H)-carboxylate as a brown oil. 1H NMR (600 MHz, CDCl3-D6) 7.40-7.30 (m, 5H); 5.13 (s, 2H); 4.80 (d, 1H); 3.95 (s, 2H); 3.60 (s, 2H); 2.10 (s, 2H); 0.20 (s, 9H).

Workup

additionAfter the addition
customwas consumed completely
additionThe reaction mixture was poured into aqueous NaHCO3 (5% w/v) at 0° C.
stirringwith vigorous stirring
extractionextracted with petroleum ether (3 L, 1 L)
dry with materialThe organic layer was dried over sodium sulfate
concentrationconcentrated

Sources & evidence

ORD record: ord-fab0f0ef73624246b01672df4297e64a
Source dataset: uspto-grants-2012_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08183245B2

Reaction notes

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