Triethylamine → (1S,4aS,6S,7R,7aR)-6,7-epoxy-1,4a,5,6,7,7a-hexahydro-7-methyl-1-(methylcarbamoyloxy)cyclopenta[c]-pyrane-4-carboxylic acid geranyl ester

HRID 1976359Notes

Reaction equation

HRID 1976359 reaction equation
C(N(CC)CC)C.C(OP(Cl)(OCC)=O)C.[O:17]1[C@@:34]2([CH3:35])[C@@H:18]1[CH2:19][C@@H:20]1[C:25]([C:26]([OH:28])=[O:27])=[CH:24][O:23][C@@H:22]([O:29][C:30](=[O:33])[NH:31][CH3:32])[C@H:21]12.[CH3:36][C:37](=[CH:39][CH2:40][CH2:41]/[C:42](=[CH:44]/[CH2:45]O)/[CH3:43])[CH3:38]>CN(C)C1C=CN=CC=1.CCCCCC.C(OCC)(=O)C.ClCCl>[CH2:45]([O:27][C:26]([C:25]1[C@H:20]2[CH2:19][C@@H:18]3[O:17][C@:34]3([CH3:35])[C@@H:21]2[C@H:22]([O:29][C:30](=[O:33])[NH:31][CH3:32])[O:23][CH:24]=1)=[O:28])/[CH:44]=[C:42](/[CH2:41][CH2:40][CH:39]=[C:37]([CH3:38])[CH3:36])\[CH3:43]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 13139Diethyl chlorophosphateHCID 637566GeraniolHCID 18397301(1S,4aS,6S,7R,7aR)-6,7-epoxy-1,4a,5,6,7,7a-hexahydro-7-methyl-1-(methylcarbamoyloxy) cyclopenta [c]-pyrane-4-carboxylic acid

Product 1

HCID 86755114(1S,4aS,6S,7R,7aR)-6,7-epoxy-1,4a,5,6,7,7a-hexahydro-7-methyl-1-(methylcarbamoyloxy)cyclopenta[c]-pyrane-4-carboxylic acid geranyl esterYield 50%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

0.5 ml of triethylamine and 0.45 ml of diethylchlorophosphate were added to a dichloromethane solution containing 331 mg of (1S,4aS,6S,7R,7aR)-6,7-epoxy-1,4a,5,6,7,7a-hexahydro-7-methyl-1-(methylcarbamoyloxy) cyclopenta [c]-pyrane-4-carboxylic acid described in Example 1. After stirring for 30 minutes at room temperature, 0.42 ml of geraniol and 17 mg of 4-dimethylaminopyridine (to be abbreviated as DMAP) were added followed by stirring for 5 hours at room temperature. The reaction mixture was then extracted with dichloromethane. After washing the organic phase with dilute hydrochloric acid, saturated aqueous sodium bicarbonate and brine, it was dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain a colorless oil from the hexane-ethyl acetate eluate in the form of (1S,4aS,6S,7R,7aR)-6,7-epoxy-1,4a,5,6,7,7a-hexahydro-7-methyl-1-(methylcarbamoyloxy) cyclopenta [c]-pyrane-4-carboxylic acid geranyl ester (280 mg, yield: 50%). The physicochemical properties of this compound are described in Table 2, Compound No. 6.

Workup

  1. stirringby stirring for 5 hours at room temperature
  2. extractionThe reaction mixture was then extracted with dichloromethane
  3. washAfter washing the organic phase with dilute hydrochloric acid, saturated aqueous sodium bicarbonate and brine, it
  4. dry with materialwas dried over anhydrous magnesium sulfate
  5. distillationAfter distilling off the solvent under reduced pressure
  6. customthe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-99e280e175e94a3a9aa91ed7326aed99
Source dataset
uspto-grants-2001_05
Patent number
US06225478B1

Reaction notes

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