1998/06/11 by Kenji Arakawa, Tadashi Eguchi, Shizuko Kakinuma · 2 citations
Biochemistry, Genetics and Molecular Biology · Chemistry · #Acyclic diene metathesis #Carbohydrate Chemistry and Synthesis #Catalysis #Chemistry #Diene #Grubbs' catalyst #Lipid Membrane Structure and Behavior #Metathesis #Olefin fiber #Organic chemistry #Polymerization #Ring-closing metathesis #Ring-opening metathesis polymerisation #Ruthenium #Salt metathesis reaction #Synthetic Organic Chemistry Methods #Yield (engineering)
paper · doi:10.1021/jo980472k
openalex publication_date 1998/06/11 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01
An olefin metathesis approach, which has been successfully applied to an efficient synthesis of archaeal 36- and 72-membered macrocyclic membrane lipids ( 1, 2a, and 2b ), is reported. In the presence of a Grubbs' ruthenium−alkylidene complex, RuCl 2 ( CHPh)(PCy 3 ) 2 ( 3 ), a ring-closing metathesis (RCM) reaction of α,ω-diene 5 efficiently proceeded in 79% yield under high dilution conditions to give 36-membered 6 . By changing the reaction conditions, a acyclic diene metathesis (ADM) product 7 was predominantly formed from the same substrate 5 . The acyclic product 7 was subsequently subjected to the RCM reaction under high dilution conditions to provide 72-membered compound 8 in 45% yield. Final catalytic hydrogenation of 6 and 8 afforded the 36-membered lipid 1 and a mixture of the 72-membered lipid 2a and 2b, respectively. The present synthetic method appears to be of significant advantage for the synthesis of such giant ring structures of the 36- and 72-membered lipids, because both of the macrocylic lipids can be obtained in a short step at will from the same starting material only by changing the order and conditions of the metathesis reaction.