Triphenylphosphine → 6-[6-Methoxy-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro-isobenzofuran-5-yl]-4-methyl-hex-4-enoic Acid Methyl Ester

HRID 910503Notes

Reaction equation

HRID 910503 reaction equation
[CH3:1][O:2][C:3](=[O:24])[CH2:4][CH2:5][C:6]([CH3:23])=[CH:7][CH2:8][C:9]1[C:10]([OH:22])=[C:11]2[C:15](=[C:16]([CH3:20])[C:17]=1[O:18][CH3:19])[CH2:14][O:13][C:12]2=[O:21].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[CH3:56][Si:57]([CH3:62])([CH3:61])[CH2:58][CH2:59]O>C1COCC1>[CH3:1][O:2][C:3](=[O:24])[CH2:4][CH2:5][C:6]([CH3:23])=[CH:7][CH2:8][C:9]1[C:10]([O:22][CH2:59][CH2:58][Si:57]([CH3:62])([CH3:61])[CH3:56])=[C:11]2[C:15](=[C:16]([CH3:20])[C:17]=1[O:18][CH3:19])[CH2:14][O:13][C:12]2=[O:21]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 180132-(Trimethylsilyl)ethanolHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 30062926-(4-Hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic acid methyl ester

Product 1

HCID 670105946-[6-Methoxy-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro-isobenzofuran-5-yl]-4-methyl-hex-4-enoic Acid Methyl EsterYield 86.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic acid methyl ester (222 mg, 0.66 mmol), triphenylphosphine (260 mg, 0.996 mmol), and diethyl azodicarboxylate (173 mg, 0.996 mmol) in THF (3 mL) at 0° C. was added a solution of 2-trimethylsilylethanol (142 μL, 0.996 mmol) in THF (3 mL). The resulting yellow solution was allowed to warm to room temperature and stirred overnight. The reaction was concentrated to dryness and ether and hexanes were added. Triphenylphosphine oxide was removed by filtration and the filtrate was concentrated and purified by silica gel chromatography to provide 248 mg of the desired product as a colorless oil. 1H NMR (300 MHz, CDCl3) δ 0.03 (s, 9H), 1.18-1.30 (m, 2H), 1.81 (s, 3H), 2.18 (s, 3H), 2.25-2.33 (m, 2H), 2.37-2.45 (m, 2H), 3.42 (d, 2H, J=7 Hz), 3.62 (s, 3H), 3.77 (s, 3H), 4.25-4.35 (m, 2H), 5.13 (s, 2H), 5.12-5.22 (m, 1H) ppm.

Workup

  1. concentrationThe reaction was concentrated to dryness and ether and hexanes
  2. additionwere added
  3. customTriphenylphosphine oxide was removed by filtration
  4. concentrationthe filtrate was concentrated
  5. custompurified by silica gel chromatography

Sources & evidence

ORD record
ord-1810a795302945d88b449d9af9b2880d
Source dataset
uspto-grants-2011_09
Patent number
US08022083B2

Reaction notes

Loading…