Ethylacetate heptane → HCID 69244355, compound

HRID 854647Notes

Reaction equation

HRID 854647 reaction equation
[CH2:1]([C:4]([O:15][CH2:16][C@H:17]1[CH2:22][CH2:21][CH2:20][C@@H:19]([O:23][CH2:24][O:25][CH3:26])[CH2:18]1)([CH2:12][CH:13]=[CH2:14])[C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6])C=C.CCCCCCC.C(OCC)(=O)C>ClCCl.Cl[Ru](=CC1C=CC=CC=1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)([P](C1CCCCC1)(C1CCCCC1)C1CCCCC1)Cl>[CH3:26][O:25][CH2:24][O:23][C@@H:19]1[CH2:20][CH2:21][CH2:22][C@H:17]([CH2:16][O:15][C:4]2([C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6])[CH2:1][CH2:14][CH2:13][CH2:12]2)[CH2:18]1

Participants

5

Reactant 2

HCID 21899848Ethylacetate heptaneHCID 69243536HCID 69243536, compound

Product 1

HCID 69244355HCID 69244355, compoundYield 76.9%

Reagents, catalysts & solvents 2

HCID 178479819HCID 178479819, compoundCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

140 mg of tert-butyl 2-allyl-2-(cis-3-methoxymethoxycyclohexylmethoxy)pent-4-enoate are dissolved in 5 ml of dichloromethane, 10 mg of Grubbs catalyst (Cl2(Cy3P)2Ru═CHPh) are added under an Ar atmosphere and the mixture is stirred at 40° C. for 48 h. 10 ml of heptane/ethyl acetate (3/1) are added and the solution is filtered through silica gel. This gives 100 mg of tert-butyl 1-(cis-3-methoxymethoxy-cyclohexylmethoxy)cyclopent-3-enecarboxylate as a brown oil. This is dissolved in 2 ml of MeOH, degassed and saturated with Ar. 30 mg of Pd/C (10%) are then added, and the mixture is degassed again. The solution is saturated with hydrogen and stirred at room temperature overnight. Dilution with 20 ml of ethyl acetate and filtration through Celite give 100 mg of crude tert-butyl 1-(cis-3-methoxymethoxycyclohexylmethoxy)cyclopentane-carboxylate. This is taken up in 2 ml of tetrahydrofuran, 0.5 ml of HCl (conc.) is added and the mixture is stirred at room temperature overnight. The solution is neutralized with saturated NaHCO3 solution and extracted three times with ethyl acetate. The organic phases are dried over MgSO4 and concentrated. Chromatography of the residue on silica gel (heptane/ethyl acetate 10/1->1/1) gives 57 mg of tert-butyl 1-(cis-3-hydroxycyclohexylmethoxy)cyclopentanecarboxylate as a yellow oil. For the next step, this is used in crude form.

Workup

  1. filtrationthe solution is filtered through silica gel
  2. dissolutionThis is dissolved in 2 ml of MeOH
  3. customdegassed and saturated with Ar
  4. addition30 mg of Pd/C (10%) are then added
  5. customthe mixture is degassed again
  6. stirringstirred at room temperature overnight
  7. filtrationDilution with 20 ml of ethyl acetate and filtration through Celite

Sources & evidence

ORD record
ord-0062712d9d374e0b854f49697a739928
Source dataset
uspto-grants-2007_08
Patent number
US07259177B2

Reaction notes

Loading…