Diethyl Malonate → ethyl 10-[(3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-yl]-2-(4,4,5,5,5-pentafluoropentyl)-8-decenoate

HRID 398071Notes

Reaction equation

HRID 398071 reaction equation
[F:1][C:2]([F:23])([C:19]([F:22])([F:21])[F:20])[CH2:3][CH2:4][CH2:5][CH:6]([CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH:17]=[CH2:18])[C:7]([O:9][CH2:10][CH3:11])=[O:8].ICCCC(F)(F)C(F)(F)F.C(OCC)(=O)CC(OCC)=O.ICCCCCC=C.[CH3:54][O:55][C:56]1[CH:65]=[C:64]2[C:59]([C@H:60]([CH2:75]C=C)[C@@:61]([C:67]3[CH:72]=[CH:71][C:70]([O:73][CH3:74])=[CH:69][CH:68]=3)([CH3:66])[CH2:62][S:63]2)=[CH:58][CH:57]=1>ClCCl.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.C1C=CC(C=[Ru](Cl)Cl)=CC=1>[CH3:54][O:55][C:56]1[CH:65]=[C:64]2[C:59]([C@H:60]([CH2:75][CH:18]=[CH:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH:6]([CH2:5][CH2:4][CH2:3][C:2]([F:23])([F:1])[C:19]([F:20])([F:21])[F:22])[C:7]([O:9][CH2:10][CH3:11])=[O:8])[C@@:61]([C:67]3[CH:68]=[CH:69][C:70]([O:73][CH3:74])=[CH:71][CH:72]=3)([CH3:66])[CH2:62][S:63]2)=[CH:58][CH:57]=1

Participants

8

Reactant 5

HCID 7761Diethyl MalonateHCID 106328827-Iodohept-1-eneHCID 12015790(3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methyl-4-(2-propenyl)thiochromanHCID 120170571,1,1,2,2-Pentafluoro-5-iodopentaneHCID 12043782Ethyl 2-(4,4,5,5,5-pentafluoropentyl)-8-nonenoate

Product 1

HCID 86588624ethyl 10-[(3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-yl]-2-(4,4,5,5,5-pentafluoropentyl)-8-decenoateYield 72%

Reagents, catalysts & solvents 2

HCID 11967259Benzylidenebis(tricyclohexylphosphine)dichlororutheniumCatalystHCID 6344DichloromethaneSolvent

Procedure

Ethyl 2-(4,4,5,5,5-pentafluoropentyl)-8-nonenoate was separately prepared from 1-iodo-4,4,5,5,5-pentafluoropentane, diethyl malonate and 1-iodo-6-heptene. A solution of this compound (4.55 g, 13.21 mmol), (3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methyl-4-(2-propenyl)thiochroman (2.5 g, 7.342 mmol) and benzylidene-bis(tricyclohexylphosphine)dichlororuthenium (302 mg, 0.367 mmol) in dichloromethane (60 ml) was heated under reflux for 6 hours. After the reaction was completed, the solvent was distilled off and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30) to give ethyl 10-[(3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-yl]-2-(4,4,5,5,5-pentafluoropentyl)-8-decenoate (3.46 g, Yield 72%) as an oil.

Workup

  1. temperatureunder reflux for 6 hours
  2. distillationthe solvent was distilled off
  3. customthe resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30)

Sources & evidence

ORD record
ord-fa689865b1124a31a006ffd53beecd19
Source dataset
uspto-grants-2003_08
Patent number
US06610733B2

Reaction notes

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