Nitrogen → tert-Butyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydropyridine-1(2H)-carboxylate

HRID 454889노트

반응식

HRID 454889 반응식
[CH3:1][C:2]1([CH3:17])[C:6]([CH3:8])([CH3:7])[O:5][B:4](B2OC(C)(C)C(C)O2)[O:3]1.C([O-])(=O)C.[K+].N#N.FC(F)(F)S(O[C:31]1[CH2:32][CH2:33][CH2:34][N:35]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH:36]=1)(=O)=O.FC(F)(F)S(O[C:52]1[CH2:53][N:54]([C:58]([O:60][C:61]([CH3:64])([CH3:63])[CH3:62])=[O:59])[CH2:55][CH2:56][CH:57]=1)(=O)=O>O1CCOCC1.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].CCOC(C)=O.CCCCCC>[CH3:17][C:2]1([CH3:1])[C:6]([CH3:7])([CH3:8])[O:5][B:4]([C:33]2[CH2:34][N:35]([C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:36][CH2:31][CH:32]=2)[O:3]1.[CH3:17][C:2]1([CH3:1])[C:6]([CH3:7])([CH3:8])[O:5][B:4]([C:52]2[CH2:57][CH2:56][CH2:55][N:54]([C:58]([O:60][C:61]([CH3:64])([CH3:63])[CH3:62])=[O:59])[CH:53]=2)[O:3]1

참가 물질

10

반응물 5

HCID 947NitrogenHCID 517044Potassium AcetateHCID 10980453tert-Butyl 5-(((trifluoromethyl)sulfonyl)oxy)-3,4-dihydropyridine-1(2H)-carboxylateHCID 210362204,4,4',4',5,5,5'-Heptamethyl-2,2'-bi(1,3,2-dioxaborolane)HCID 53978067tert-Butyl 3-(((trifluoromethyl)sulfonyl)oxy)-5,6-dihydropyridine-1(2H)-carboxylate

생성물 2

HCID 49835909Tert-butyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 59327225tert-Butyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydropyridine-1(2H)-carboxylate수율 62.1%

시약·촉매·용매 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 312751,4-Dioxane용매2회HCID 21226206Ethyl acetate hexane용매

반응 조건

온도
80 °C

실험 절차

A flask with 4,4,4′,4′,5,5,5′-heptamethyl-2,2′-bi(1,3,2-dioxaborolane) (10.48 g, 43.7 mmol), (dppf)PdCl2 (0.930 g, 1.139 mmol), and potassium acetate (11.18 g, 114 mmol) was flushed with N2 (3×), then 1,4-dioxane (100 mL) was added followed by a solution of tert-butyl 5-(trifluoromethylsulfonyloxy)-3,4-dihydropyridine-1(2H)-carboxylate and tert-butyl 3-(trifluoromethylsulfonyloxy)-5,6-dihydropyridine-1(2H)-carboxylate (1:1 ratio, 12.58 g, 38.0 mmol) in 1,4-dioxane (100 mL). The solution was heated in an 80° C. oil bath for 20 hours. The reaction was quenched with water (100 mL) and the aqueous layer extracted with EtOAc (3×100 mL). The combined organic layers were washed with saturated aqueous NaCl (100 mL), dried with magnesium sulfate (MgSO4), and concentrated. The residue was purified by silica gel chromatography using ISCO™ (330 g SiO2, O-20% EtOAc/hexane) to give tert-butyl 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1(2H)-carboxylate and tert-butyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-dihydropyridine-1(2H)-carboxylate (7.29 g, 23.58 mmol, 62.1% yield) (inseparable 2:1 mixture of olefin regioisomers) as a white solid.

후처리

  1. customThe reaction was quenched with water (100 mL)
  2. extractionthe aqueous layer extracted with EtOAc (3×100 mL)
  3. washThe combined organic layers were washed with saturated aqueous NaCl (100 mL)
  4. dry with materialdried with magnesium sulfate (MgSO4)
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel chromatography

출처 및 근거

ORD 기록
ord-0a68684428ed4627a31582c91a14fd9f
출처 데이터셋
uspto-grants-2013_07
특허 번호
US08497265B2

반응 노트

불러오는 중…