Water → 3-Benzo[1,3]dioxol-5-yl-4-(3-(2-{2-[2-(2-aminoethoxy)ethoxy]ethoxy}ethoxy)-4,5-dimethoxybenzyl)-5-hydroxy-5-(4-methoxyphenyl)-5H-furan-2-one

HRID 1510972Notes

Reaction equation

HRID 1510972 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3[C:11](=[O:50])[O:12][C:13]([OH:49])([C:41]4[CH:46]=[CH:45][C:44]([O:47][CH3:48])=[CH:43][CH:42]=4)[C:14]=3[CH2:15][C:16]3[CH:21]=[C:20]([O:22][CH3:23])[C:19]([O:24][CH3:25])=[C:18]([O:26][CH2:27][CH2:28][O:29][CH2:30][CH2:31][O:32][CH2:33][CH2:34][O:35][CH2:36][CH2:37][N:38]=[N+]=[N-])[CH:17]=3)=[CH:9][C:4]=2[O:3][CH2:2]1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>C1COCC1>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]3[C:11](=[O:50])[O:12][C:13]([OH:49])([C:41]4[CH:46]=[CH:45][C:44]([O:47][CH3:48])=[CH:43][CH:42]=4)[C:14]=3[CH2:15][C:16]3[CH:21]=[C:20]([O:22][CH3:23])[C:19]([O:24][CH3:25])=[C:18]([O:26][CH2:27][CH2:28][O:29][CH2:30][CH2:31][O:32][CH2:33][CH2:34][O:35][CH2:36][CH2:37][NH2:38])[CH:17]=3)=[CH:9][C:4]=2[O:3][CH2:2]1

Participants

5

Reactant 3

HCID 962WaterHCID 11776TriphenylphosphineHCID 866321203-Benzo[1,3]dioxol-5-yl-4-(3-(2-{2-[2-(2-azidoethoxy)ethoxy]ethoxy}ethoxy)-4,5-dimethoxybenzyl)-5-hydroxy-5-(4-methoxyphenyl)-5H-furan-2-one

Product 1

HCID 689426823-Benzo[1,3]dioxol-5-yl-4-(3-(2-{2-[2-(2-aminoethoxy)ethoxy]ethoxy}ethoxy)-4,5-dimethoxybenzyl)-5-hydroxy-5-(4-methoxyphenyl)-5H-furan-2-oneYield 17.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of 1.49 g (2.15 mmol) of 3-Benzo[1,3]dioxol-5-yl-4-(3-(2-{2-[2-(2-azidoethoxy)ethoxy]ethoxy}ethoxy)-4,5-dimethoxybenzyl)-5-hydroxy-5-(4-methoxyphenyl)-5H-furan-2-one 9 and 1.00 g (3.00 mmol) of polymer bound PPh3 (polystyrene, 2% DVB, FLUKA) was suspended in 10 ml of THF and stirred at room temperature overnight. Water is added (200 μl, ≈10 mmol) and stirring was continued for 3 d. The polymer was removed by filtration and the filtrate was evaporated in vacuo. The remaining oil was purified by silica gel column chromatography (EtOAc/MeOH/NEt3 5/1/0.3), yielding 246 mg of the product (0.37 mmol, 17%). 1H-NMR (CDCl3) δ=7.32 (d, 2H, J=8.1 Hz), 6.83, (m, 2H), 6.75 (d, 2H, J=8.1 Hz), 6.68 (d, 1H, J=7.7 Hz), 6.14 (s, 1H), 5.91 (s, 1H), 5.85 (s, 2H), 3.88 (m, 2H), 3.70 (s, 4H), 3.64 (s, 3H), 3.59 (m, 4H), 3.54 (s, 3H), 3.48 (m, 4H) 3.37 (m, 2H), 3.15 (m, 2H) ppm. The protons of the butenolide hydroxy group and the amino function were not detected. 13C-NMR δ=171.2, 160.8, 160.1, 152.8, 151.9, 147.9, 147.5, 137.2, 131.8, 129.2, 127.8, 127.4, 123.2, 123.1, 113.7, 109.4, 108.5, 108.2, 106.6, 106.0, 101.2, 70.6, 70.4, 70.3, 70.2, 69.8, 69.7, 68.6, 60.6, 55.8, 55.2, 40.0, 32.0 ppm. MS: m/z=690 [M+Na]+, 668 [M+H]+. Elemental or HRMS analysis could not be obtained from this product.

Workup

  1. stirringstirring
  2. waitwas continued for 3 d
  3. customThe polymer was removed by filtration
  4. customthe filtrate was evaporated in vacuo
  5. customThe remaining oil was purified by silica gel column chromatography (EtOAc/MeOH/NEt3 5/1/0.3)

Sources & evidence

ORD record
ord-15a6156cb55741a09e3cada6885bddba
Source dataset
uspto-grants-2012_07
Patent number
US08212058B2

Reaction notes

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