Dimethyl Carbonate → 3-(1-methylpyrrolidin-2-yl)-4H-pyridine-1-carboxylic acid methyl ester

To a solution of dimethyl carbonate (0.05 mL, 0.6 mmol) in 2 mL of dry THF was slowly added 3-(1-methylpyrrolidin-2-yl)-1,4-bis-trimethylsilanyl-1,4-dihydropyridine I (0.2 mL, 0.68 mmol). A solution of TBAF in THF (0.06 mL, 0.06 mmol) was then introduced dropwise and the reaction mixture was stirred at RT for 1 h. The reaction was quenched with a saturated aqueous solution of NaHCO3. The aqueous layer was extracted with ether (2 times), and the combined organic layers were washed with brine and dried over K2CO3. The solvent was removed under reduced pressure and the crude material was purified by RPLC (hexanes) to afford 0.1374 g (91%) of 3-(1-methylpyrrolidin-2-yl)-4H-pyridine-1-carboxylic acid methyl ester II as a clear oil. IR (thin film, neat, NaCl): 2949, 2826, 2764, 1721, 1695, 1437, 1334, 1313, 1194, 983 cm−1. 1H NMR (300 MHz, CDCl3): δ 6.68–6.51 (m, 2 H), 4.88–4.77 (m, 1 H), 3.65 (s, 3 H), 2.95–2.91 (m, 1 H), 2.64–2.62 (m, 2 H), 2.41–2.33 (m, 1 H), 2.05–1.93 (m, 5 H), 1.68–1.53 (m, 4 H); 13C NMR (CDCl3, 75 MHz) δ 151.81, 123.15, 122.74, 120.28, 119.63, 118.08, 117.71, 106.22, 105.94, 70.37, 56.60, 53.05, 40.16, 40.08, 28.76, 28.38, 22.37, 21.56, 21.05. HRMS Calcd for C12H18N2O2: 223.1447 [M+H]+. Found: 223.1434 [M+H]+. [α]24D−65.5 (c=8, CH2Cl2).

1. customThe reaction was quenched with a saturated aqueous solution of NaHCO3
2. extractionThe aqueous layer was extracted with ether (2 times)
3. washthe combined organic layers were washed with brine
4. dry with materialdried over K2CO3
5. customThe solvent was removed under reduced pressure
6. customthe crude material was purified by RPLC (hexanes)

ORD 기록

ord-16cb0573d5ce4f0885f06a7f9e98ceb1

출처 데이터셋

uspto-grants-2006_02

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US06995265B2