Nitrogen → HCID 54034338, 화합물

HRID 2095322

반응식

HRID 2095322 반응식
[C:1]([O:5][C:6]([N:8]1[CH2:11][CH2:10][C@@H:9]1[CH2:12][OH:13])=[O:7])([CH3:4])([CH3:3])[CH3:2].[Br:14][C:15]1[CH:16]=[N:17][CH:18]=[C:19](O)[CH:20]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N#N.N(C(OC(C)C)=O)=NC(OC(C)C)=O.N(C(OC(C)C)=O)NC(OC(C)C)=O>C1COCC1.C1(C)C=CC=CC=1>[Br:14][C:15]1[CH:16]=[N:17][CH:18]=[C:19]([O:13][CH2:12][C@H:9]2[CH2:10][CH2:11][N:8]2[C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH:20]=1

참가 물질

9

반응물 6

HCID 947NitrogenHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 88220Diisopropyl bicarbamateHCID 5995293-Bromo-5-hydroxypyridineHCID 11074142(R)-1-Boc-2-azetidinemethanol

생성물 1

HCID 54034338HCID 54034338, 화합물수율 56%

시약·촉매·용매 2

HCID 1140Toluene용매HCID 8028Tetrahydrofuran용매

실험 절차

[1-(tert-Butoxycarbonyl)-2(R)-azetidinyl]methanol (1.42 g, 7.60 mmol) was dried by azeotropic evaporation with toluene (3×10 mL) in a 50 mL round-bottom flask. 3-Bromo-5-hydroxypyridine (1.32 g, 7.60 mmol) and triphenylphosphine (2.20 g, 8.40 mmol, 1.1 equiv.) were added. The flask was capped with a rubber septum, and the atmosphere was exchanged three times with N2 (balloon). Anhydrous THF (25 mL) was added via syringe, and the mixture was stirred in an ice bath until all reagents were dissolved. Diisopropyl azodicarboxylate (DIAD, 1.76 mL, 8.40 mmol, 1.1 equiv.) was added dropwise in several portions over 30 min. The resulting mixture was stirred in the thawing ice bath overnight. After removal of the THF, the residue was purified by CC on SiO2 (25×3.8 cm, EtOAc/hexanes 1:4 to 3:7) to give crude product. A 1H NMR spectrum showed that the material was a mixture with diisopropyl hydrazodicarboxylate (containing approx. 56% of the title compound by mass), which was used directly for the next step. 1H NMR (CDCl3, 400 MHz; signals of the title compound only) δ 8.29 (d, 1H, J=1.8 Hz), 8.28 (d, 1H, J=2.7 Hz), 7.43 (t, 1H, J=2.3 Hz), 4.55-4.47 (m, 1H), 4.33 (br s, 1H), 4.13-4.09 (m, 1H), 3.93-3.85 (m, 2H), 2.40-2.20 (m, 2H), 1.43 (s, 9H).

후처리

  1. customThe flask was capped with a rubber septum
  2. dissolutionwere dissolved
  3. stirringThe resulting mixture was stirred in the thawing ice bath overnight
  4. customAfter removal of the THF
  5. customthe residue was purified by CC on SiO2 (25×3.8 cm, EtOAc/hexanes 1:4 to 3:7)
  6. customto give crude product

출처 및 근거

ORD 기록
ord-828a8ba7c01044be92aec86547898904
출처 데이터셋
uspto-grants-2013_05
특허 번호
US08445684B2

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