Potassium Acetate → 5-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole

HRID 538990

반응식

HRID 538990 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:12]=[CH:11][N:10]([CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])[N:9]=2)=[CH:4][CH:3]=1.Br[C:22]1[CH:27]=[CH:26][C:25]([C:28]2[N:32]([CH2:33][O:34][CH2:35][CH2:36][Si:37]([CH3:40])([CH3:39])[CH3:38])[N:31]=[CH:30][N:29]=2)=[CH:24][CH:23]=1.C([O-])(=O)C.[K+].[CH3:46][C:47]1([CH3:63])[C:51]([CH3:53])([CH3:52])[O:50][B:49]([B:54]2[O:58][C:57]([CH3:60])([CH3:59])[C:56]([CH3:62])([CH3:61])[O:55]2)[O:48]1>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.[Fe+2]>[CH3:46][C:47]1([CH3:63])[C:51]([CH3:53])([CH3:52])[O:50][B:49]([C:2]2[CH:7]=[CH:6][C:5]([C:8]3[N:12]=[CH:11][N:10]([CH2:13][O:14][CH2:15][CH2:16][Si:17]([CH3:20])([CH3:19])[CH3:18])[N:9]=3)=[CH:4][CH:3]=2)[O:48]1.[CH3:60][C:57]1([CH3:59])[C:56]([CH3:61])([CH3:62])[O:55][B:54]([C:22]2[CH:23]=[CH:24][C:25]([C:28]3[N:32]([CH2:33][O:34][CH2:35][CH2:36][Si:37]([CH3:40])([CH3:39])[CH3:38])[N:31]=[CH:30][N:29]=3)=[CH:26][CH:27]=2)[O:58]1

참가 물질

8

반응물 4

HCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 595259995-(4-bromophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazoleHCID 595262653-(4-bromophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole

생성물 2

HCID 595255703-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazoleHCID 680888445-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole수율 98%

시약·촉매·용매 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)촉매HCID 312751,4-Dioxane용매

반응 조건

온도
90 °C

실험 절차

In a sealed tube, a mixture of 3-(4-bromophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole and 5-(4-bromophenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole (5.00 g, 14.1 mmol), DPPF (0.469 g, 0.847 mmol), PdCl2dppf-dichloromethane (1.38 g, 1.69 mmol), potassium acetate (4.15 g, 42.3 mmol) and 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (7.17 g, 28.2 mmol) in dioxane (141 mL) was heated at 90° C. under N2 for 18 hours. The crude product was filtered through a pad of Celite, washed with saturated NaHCO3, brine, dried over MgSO4, filtered, and concentrated. Purification of the crude material by column chromatography, eluting with 0-30% EtOAc/Hexanes, afforded 3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole and 5-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-1,2,4-triazole (5.55 g, 98%) as a mixture of two regioisomers. LCMS (APCI+) m/z 402 [M+H]+.

후처리

  1. filtrationThe crude product was filtered through a pad of Celite
  2. washwashed with saturated NaHCO3, brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification of the crude material by column chromatography
  7. washeluting with 0-30% EtOAc/Hexanes

출처 및 근거

ORD 기록
ord-8fe734810f74453ca4058948523960ef
출처 데이터셋
uspto-grants-2014_10
특허 번호
US08865726B2

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