4-Vinylpyridine → (R)-(-)-5'-(2-(4-Pyridyl)ethenyl)spiro[1-azabicyclo[2.2.2]octane-3,2'(3'H)-furo[2,3-b]pyridine]

HRID 49613

반응식

HRID 49613 반응식
Br[C:2]1[CH:3]=[C:4]2[CH2:10][C@:9]3([CH:15]4[CH2:16][CH2:17][N:12]([CH2:13][CH2:14]4)[CH2:11]3)[O:8][C:5]2=[N:6][CH:7]=1.[CH:18]([C:20]1[CH:25]=[CH:24][N:23]=[CH:22][CH:21]=1)=[CH2:19].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N:23]1[CH:24]=[CH:25][C:20]([CH:18]=[CH:19][C:2]2[CH:3]=[C:4]3[CH2:10][C@:9]4([CH:15]5[CH2:16][CH2:17][N:12]([CH2:13][CH2:14]5)[CH2:11]4)[O:8][C:5]3=[N:6][CH:7]=2)=[CH:21][CH:22]=1

참가 물질

7

반응물 4

HCID 75024-VinylpyridineHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 54506690(2R)-5'-bromo-3'H-spiro[4-azabicyclo[2.2.2]octane-2,2'-furo[2,3-b]pyridine]

생성물 1

HCID 53757590(R)-(-)-5'-(2-(4-Pyridyl)ethenyl)spiro[1-azabicyclo[2.2.2]octane-3,2'(3'H)-furo[2,3-b]pyridine]수율 72%

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 6342Acetonitrile용매

반응 조건

온도
102.5 °C

실험 절차

(R)-(−)-5′-Bromospiro[1-azabicyclo[2.2.2]octane-3,2′(3′H)-furo[2,3-b]pyridine] (295 mg, 1 mmol), 4-vinylpyridine (0.135 mL, 1.25 mmol), palladium(II)acetate (7.2 mg, 0.032 mmol), tri-o-tolylphosphine (38.7 mg, 0.127 mmol), and triethylamine (0.5 mL, 3.6 mmol) in anhydrous acetonitrile (0.5 mL) were combined in a heavy-walled threaded glass tube containing a magnetic stir bar, purged with argon and sealed with a Teflon plug and FETFE O-ring. The mixture was stirred and heated at 100 to 105° C. for 48 hours, cooled to room temperature, dissolved in chloroform (25 mL), washed with saturated aqueous sodium carbonate (2 mL), dried (MgSO4), and evaporated under reduced pressure. Purification by flash chromatography through silica gel (eluting with ammoniated chloroform/methanol, 95:5), followed by recrystallization from acetone afforded the title compound (230 mg, 0.72 mmol, 72%): electrospray MS (m/z, relative intensity) 320 ([MH]+, 100).

후처리

  1. additioncontaining a magnetic stir bar
  2. custompurged with argon
  3. customsealed with a Teflon plug and FETFE O-ring
  4. temperaturecooled to room temperature
  5. dissolutiondissolved in chloroform (25 mL)
  6. washwashed with saturated aqueous sodium carbonate (2 mL)
  7. dry with materialdried (MgSO4)
  8. customevaporated under reduced pressure
  9. customPurification by flash chromatography through silica gel (eluting with ammoniated chloroform/methanol, 95:5)
  10. customfollowed by recrystallization from acetone

출처 및 근거

ORD 기록
ord-34ce5c0d9f7c4dfd97e2ec1e88b787b9
출처 데이터셋
uspto-grants-2004_03
특허 번호
US06706878B2

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