Methyl Acrylate → methyl (2E,5R)-6-(benzyloxy)-5-(2,2-diethoxyethoxy)hex-2-enoate

HRID 716658Notes

Reaction equation

HRID 716658 reaction equation
[CH2:1]([O:3][CH:4]([O:20][CH2:21][CH3:22])[CH2:5][O:6][C@H:7]([CH2:17][CH:18]=[CH2:19])[CH2:8][O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[CH3:2].[C:23]([O:27][CH3:28])(=[O:26])C=C>ClCCl.CC1C=C(C)C(N2C(=[Ru](Cl)(Cl)=CC3C=CC=CC=3)N(C3C(C)=CC(C)=CC=3C)CC2)=C(C)C=1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1>[CH2:10]([O:9][CH2:8][C@H:7]([O:6][CH2:5][CH:4]([O:3][CH2:1][CH3:2])[O:20][CH2:21][CH3:22])[CH2:17]/[CH:18]=[CH:19]/[C:23]([O:27][CH3:28])=[O:26])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

5

Reactant 2

HCID 7294Methyl AcrylateHCID 59281174[(R)-2-(2,2-diethoxyethoxy)-4-pentenyloxymethyl]benzene

Product 1

HCID 86729528methyl (2E,5R)-6-(benzyloxy)-5-(2,2-diethoxyethoxy)hex-2-enoate

Reagents, catalysts & solvents 2

HCID 11147261(1,3-Dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

This reaction was carried out in 10 batches. To a solution of C2 (10 g, 32 mmol) in dichloromethane (400 mL) was added [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium (Grubbs 2nd-generation catalyst, 1.38 g, 1.62 mmol) and methyl prop-2-enoate (69.7 g, 0.81 mol), and the reaction mixture was stirred at room temperature for 18 hours. Solvent was removed in vacuo, and the residue was purified via silica gel chromatography (Eluent: 3:1 petroleum ether/ethyl acetate) to provide the product as a yellow oil. Combined yield: 70 g, 0.19 mol, 59%. 1H NMR (400 MHz, CDCl3) δ 7.27-7.38 (m, 5H), 6.94-7.04 (m, 1H), 5.89 (br d, J=15.6 Hz, 1H), 4.58 (dd, J=5.3, 5.0 Hz, 1H), 4.54 (s, 2H), 3.73 (s, 3H), 3.44-3.7 (m, 9H), 2.41-2.55 (m, 2H), 1.21 (t, J=7.0 Hz, 3H), 1.20 (t, J=7.0 Hz, 3H).

Workup

  1. customSolvent was removed in vacuo
  2. customthe residue was purified via silica gel chromatography (Eluent: 3:1 petroleum ether/ethyl acetate)

Sources & evidence

ORD record
ord-100ed55f879e49aeb1ddaac65bf3accf
Source dataset
uspto-grants-2015_11
Patent number
US09192612B2

Reaction notes

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