Potassium Carbonate → tert-Butyl 4-(4-(((benzyloxy)carbonyl)amino)-3-ethylphenyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 2272427노트

반응식

HRID 2272427 반응식
C(=O)([O-])[O-].[K+].[K+].CC1(C)C(C)(C)OB([C:15]2[CH2:20][CH2:19][N:18]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:17][CH:16]=2)O1.Br[C:30]1[CH:35]=[CH:34][C:33]([NH:36][C:37](=[O:46])[O:38][CH2:39][C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)=[C:32]([CH2:47][CH3:48])[CH:31]=1>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.CN(C=O)C>[CH2:39]([O:38][C:37]([NH:36][C:33]1[CH:34]=[CH:35][C:30]([C:15]2[CH2:20][CH2:19][N:18]([C:21]([O:23][C:24]([CH3:25])([CH3:26])[CH3:27])=[O:22])[CH2:17][CH:16]=2)=[CH:31][C:32]=1[CH2:47][CH3:48])=[O:46])[C:40]1[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=1

참가 물질

6

반응물 3

HCID 11430Potassium CarbonateHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 71232504benzyl N-(4-bromo-2-ethylphenyl)carbamate

생성물 1

HCID 71232505tert-Butyl 4-(4-(((benzyloxy)carbonyl)amino)-3-ethylphenyl)-5,6-dihydropyridine-1(2H)-carboxylate수율 57.2%

시약·촉매·용매 2

HCID 178418807HCID 178418807, 화합물촉매HCID 6228Dimethylformamide용매

실험 절차

Potassium carbonate (215 mg, 1.55 mmol) the tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1(2H)-carboxylate (I37) (160 mg, 0.517 mmol), benzyl (4-bromo-2-ethylphenyl)carbamate (I34) (182 mg, 0.543 mmol), PdCl2(dppf)-DCM solvate (22 mg, 5 mol %) and DMF (5 mL) were loaded into a Schlenk tube, and degassed with 3× vacuum/nitrogen cycles. The mixture was brought to 80° C. under nitrogen then after 18 hours cooled and poured into water (100 mL). DCM (75 mL) and brine (50 mL) were added, the aqueous phase was washed with further DCM (2×75 mL), and the combined DCM extracts washed with brine, dried and evaporated. Chromatography (40 g silica cartridge, 0-80% ethyl acetate/petroleum benzine 40-60° C.) gave the title compound (I39) (129 mg, 57% yield) as a colourless oil; 1H NMR (400 MHz, CDCl3) δ 7.77 (s, 1H), 7.45-7.31 (m, 5H), 7.22 (dd, J=8.5, 2.1 Hz, 1H), 7.18 (d, J=2.1 Hz, 1H), 6.48 (s, 1H), 5.99 (s, 1H), 5.21 (s, 2H), 4.06 (d, J=2.5 Hz, 2H), 3.63 (t, J=5.7 Hz, 2H), 2.58 (q, J=7.6 Hz, 2H), 2.50 (s, 2H), 1.49 (s, 9H), 1.22 (t, J=7.6 Hz, 3H). LCMS Method C: rt 6.67 min; m/z 337.1 [M-Boc+2H]+, 381.1 [M-tBu+2H]+.

후처리

  1. customdegassed with 3× vacuum/nitrogen cycles
  2. customwas brought to 80° C. under nitrogen
  3. temperatureafter 18 hours cooled
  4. additionpoured into water (100 mL)
  5. additionDCM (75 mL) and brine (50 mL) were added
  6. washthe aqueous phase was washed with further DCM (2×75 mL)
  7. washthe combined DCM extracts washed with brine
  8. customdried
  9. customevaporated

출처 및 근거

ORD 기록
ord-9fd4f3f3f1f74030adc8c2ad54d14d97
출처 데이터셋
uspto-grants-2015_09
특허 번호
US09120761B2

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