Triphenylphosphine → 2-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-[6-methoxy-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro-isobenzofuran-5-yl]-4-methyl-hex-4-enoic acid 2-trimethylsilanyl-ethyl Ester

HRID 32958

반응식

HRID 32958 반응식
[CH3:1][O:2][P:3]([CH2:7][CH:8]=[CH:9][CH2:10][CH:11]([CH2:15][C:16]([CH3:33])=[CH:17][CH2:18][C:19]1[C:20]([OH:32])=[C:21]2[C:25](=[C:26]([CH3:30])[C:27]=1[O:28][CH3:29])[CH2:24][O:23][C:22]2=[O:31])[C:12]([OH:14])=[O:13])([O:5][CH3:6])=[O:4].[CH3:34][Si:35]([CH:38](O)[CH3:39])([CH3:37])[CH3:36].C1(P([C:54]2[CH:59]=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[CH3:34][Si:35]([CH3:37])([CH3:36])[CH2:38][CH2:39][O:13][C:12](=[O:14])[CH:11]([CH2:10][CH:9]=[CH:8][CH2:7][P:3]([O:5][CH3:6])([O:2][CH3:1])=[O:4])[CH2:15][C:16]([CH3:33])=[CH:17][CH2:18][C:19]1[C:20]([O:32][CH2:54][CH2:59][Si:35]([CH3:37])([CH3:36])[CH3:34])=[C:21]2[C:25](=[C:26]([CH3:30])[C:27]=1[O:28][CH3:29])[CH2:24][O:23][C:22]2=[O:31]

참가 물질

6

반응물 4

HCID 11776Triphenylphosphine2회HCID 220568ethyl N-ethoxycarbonyliminocarbamate2회HCID 124478981-(Trimethylsilyl)ethanol2회HCID 765461892-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic Acid

생성물 1

HCID 765461912-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-[6-methoxy-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro-isobenzofuran-5-yl]-4-methyl-hex-4-enoic acid 2-trimethylsilanyl-ethyl Ester수율 85%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

A solution of 2-[4-(dimethoxy-phosphoryl)-but-2-enyl]-6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic acid (160 mg, 0.332 mmol) and trimethylsilylethanol (160 mg, 1.36 mmol) in THF (8.00 mL) was stirred with triphenylphosphine (345 mg, 1.33 mmol). To this solution was added diethyl azodicarboxylate (230 μL, 1.33 mmol) at 0° C. The mixture was allowed to warm to room temperature and stirred for 16 hours. Additional triphenylphosphine (180 mg, 0.692 mmol), trimethylsilylethanol (160 mg, 1.36 mmol), and diethyl azodicarboxylate (115 μL, 0.665 mmol) were added and the reaction mixture was stirred for another 1 day at room temperature. The reaction was worked up by removing the solvents in vacuo and purifying the residue by silica gel chromatography to provide 192 mg (85%) of the product as a clear oil. 1H NMR (300 MHz, CDCl3) δ 0.03 (s, 9H), 0.05 (s, 9H), 0.93-0.96 (m, 2H), 1.20-1.29 (m, 2H), 1.78 (s, 3H), 2.01-2.32 (m, 4H), 2.17 (s, 3H), 2.51 (d, 1H, J=22 Hz), 2.58 (d, 1H, J=22 Hz), 2.50-2.60 (m, 1H), 3.37 (d, 2H, J=7 Hz), 3.72 (d, 6H, J=11 Hz), 3.76 (s, 3H), 4.08 (appt t, 2H, J=8 Hz), 4.30 (appt t, 2H, J=8 Hz), 5.12 (s, 2H), 5.15-5.25 (m, 1H), 5.36-5.63 (m, 2H) ppm; 31P (121.4 MHz, CDCl3) δ 29.3 ppm; MS (m/z) 705.3 [M+Na]+.

후처리

  1. stirringthe reaction mixture was stirred for another 1 day at room temperature
  2. customby removing the solvents in vacuo
  3. custompurifying the residue by silica gel chromatography

출처 및 근거

ORD 기록
ord-283cb3dc8979479ca2e69c059e52ad07
출처 데이터셋
uspto-grants-2008_09
특허 번호
US07427636B2

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