26607-23-8Relevant academic research and scientific papers
Synthesis of deuterium labeled perillyl alcohol and dual C-13 and deuterium labeled perillic acid, major metabolites of d-limonene
Chen, Haitao,Chan, Kenneth K.
, p. 369 - 377 (2007/10/03)
Dual C-13 and deuterium labeled perillic acid [(1,1-dideuterio-1-13C-2-methyl)ethenyl]-1-cyclohexene-1-carboxylic acid (6) and deuterated perillyl alcohol, [(2,2-dideuterio-1-methyl)-ethenyl[-1-deuteriohydroxymethyl-1-cyclohexene(9) were synthesized from commercially available (4S)-(-)-perillaldehyde (1). Compound 1 was first protected with ethylene glycol to yield the ethylene ketal followed by oxidation with OsO4/NalO4 to cleave the terminal double bond t afford the key intermediate ketone, 4-acetyl-1-cyclohexene-1-carboxaldehyde ethylene ketal (3). 3 was then converted to the labeled perillyl aldehyde by Wittig reaction with prepared Ph313CD3l or Ph3PCD3l followed by deprotection to give the labeled perillaldehydes, [(2,2-dideuterio-2-13C-1-methyl)-ethenyl]-1-cyclohexene-1-carboxaldehyde (8). 5 was further oxidized by freshly prepared Ag2O to give the desired compound 6. 8 was reduced by LiAID4 to afford the desired compound 9. The same synthetic procedure may be adopted to synthesize the radioactive isotope labeled perillic acid and perillyl alcohol.
General scope of 1,3-dioxolanation of αβ-unsaturated aldehydes with 1,2-bis((trimethylsilyl)oxy)ethane and trimethylsilyl trifluoromethanesulfonate
Hwu, Jih Ru,Leu, Lish-Cheng,Robl, Jeffrey A.,Anderson, Denise A.,Wetzel, John M.
, p. 188 - 191 (2007/10/02)
1,3-Dioxolanation of αβ-unsaturated aldehydes with 1,2-bis((trimethylsilyl)oxy)ethane in the presence of trimethylsilyl trifluoromethanesulfonate as catalyst has been systematically investigated. These silylated reagents readily acetalize aliphatic, highly conjugated aliphatic, and aromatic enals. Under the mild, aprotic conditions of the reaction, olefins do not rearrange or isomerize, and the acid-sensitive propionyloxy, (tetrahydropyranyl)oxy, and vinyl ether moieties are relatively stable. Aromatic bromide, furan, thiophene, and nitro functionalities are also inert. The only limitation found is in the case of 4-(dimethylamino)cinnamaldehyde, which did not afford a detectable amount of the corresponding dioxolane.
