Methyl 4-oxocyclohexanecarboxylate → Methyl 4-oxocyclohexanecarboxylate

HRID 1253352Notes

Reaction equation

HRID 1253352 reaction equation
[Cr](Cl)([O-])(=O)=[O:2].[NH+]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[O:12]=[C:13]1[CH2:18][CH2:17][CH:16]([C:19]([O:21][CH3:22])=[O:20])[CH2:15][CH2:14]1>>[O:12]=[C:13]1[CH2:18][CH2:17][CH:16]([C:19]([O:21][CH3:22])=[O:20])[CH2:15][CH2:14]1.[O:2]=[CH:7][CH:8]=[C:9]1[CH2:14][CH2:15][CH:16]([C:19]([O:21][CH3:22])=[O:20])[CH2:11][CH2:10]1

Participants

4

Reactant 2

HCID 226643Methyl 4-oxocyclohexanecarboxylateHCID 178418287HCID 178418287, compound

Product 2

HCID 226643Methyl 4-oxocyclohexanecarboxylateHCID 14806116Methyl 4-(2-oxoethylidene)cyclohexane-1-carboxylate

Procedure

The epoxides used as the starting materials in the general process described above can be obtained from available starting materials using an appropriate series of reactions. Thus, methyl 4-hydroxybenzoate is hydrogenated using 5% rhodium on alumina as catalyst to give methyl 4-hydroxycyclohexanecarboxylate. This is then oxidized with pyridinium chlorochromate resulting in methyl 4-oxocyclohexanecarboxylate. The 2-carbon homologation of methyl 4-oxocyclohexanecarboxylate to give methyl 4-(oxoethylidene)cyclohexanecarboxylate is carried out using the method developed by A. I. Meyers. Acetaldehyde t-butylimine is metalated with lithium diisopropylamide and then treated with diethyl chlorophosphate to provide the lithioeneaminephosphonate. Addition of methyl 4-oxocyclohexanecarboxylate and subsequent acid hydrolysis gives methyl 4-(oxoethylidene)cyclohexanecarboxylate. The reduction of this oxoethylidene compound with sodium borohydride gives methyl 4-(2-hydroxyethylidene)cyclohexanecarboxylate.

Sources & evidence

ORD record
ord-b757459c4ace472a86bd60e5e57e2fb9
Source dataset
uspto-grants-1988_05
Patent number
US04748274

Reaction notes

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