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

HRID 2207785Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2207785
[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]>[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

Komponenten

9

Edukt 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

Produkt 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)-carboxylateAusbeute 62,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 312751,4-DioxaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

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, 0-20% 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) (inseperable 2:1 mixture of olefin regioisomers) as a white solid.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-43e67ab4f4b64eccb8fdaef474b8485b
Quelldatensatz
uspto-grants-2016_06
Patentnummer
US09376450B2

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