The discrimination between cyclomonomers and various oligomers formed during a ring-closing metathesis (RCM) process is not an easy task. Their (1)H NMR patterns are often very similar, and the use of mass spectrometry techniques is usually recommended. Here, we show that the DOSY-NMR method is a reliable tool to help in the identification of cyclomonomers versus cyclodimers by comparing the translational diffusion coefficient of the compounds issued from RCM reactions with the diffusion coefficient of their respective precursors.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1002/mrc.2808 | DOI Listing |
Org Lett
January 2025
Graduate School of Life Sciences, Tohoku University, 2-1-1 Katahira, 980-8577 Aoba-ku, Sendai, Japan.
Our efforts toward the synthesis of the marine natural product portimine are described. The key to the synthesis of the skeleton is a stereoretentive copper-catalyzed C()-C() Stille-type cross-coupling that enables the convergent assembly of functionalized fragments. The core skeleton of portimine was constructed via ring-closing metathesis and transannular acetal formation.
View Article and Find Full Text PDFACS Omega
December 2024
Division of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
A Hoveyda-Grubbs (HG)-type olefin metathesis complex with a selenoether moiety at the terminus of phenoxy moiety was synthesized. The complex showed direct selenium-atom coordination to the ruthenium center, resulting in higher thermodynamic stability compared with the parent HG catalyst. The selenium atom binding enhanced the tolerance to protic solvent molecules in ring-closing metathesis of -tosyldiallylamide and diethyl diallylmalonate, and also in the cross metathesis between 3-butenylbenzoate and methyl acrylate.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan.
(-)-Exiguolide is a marine macrolide natural product with potent anticancer activity. In this study, the total synthesis of exiguolide stereoisomers, (9)-exiguolide, (9,13)-exiguolide, and (9,13,19)-exiguolide, was achieved by capitalizing on our macrocyclization/transannular pyran cyclization strategy. The impact of the stereochemical permutation on the reactivity of advanced intermediates, the conformation of the macrocyclic skeleton, and the antiproliferative activity against human cancer cells were investigated in detail.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, and Chemical Biology Center, Peking University, 38 Xueyuan Road, Beijing 100191, China.
Angew Chem Int Ed Engl
November 2024
State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, Gansu Province, 730000, China.
Kalmanol (1) is the first isolated kalmane-type grayanoid featuring a highly oxidized 5/8/5/5 tetracyclic carbon skeleton and 9 contiguous stereocenters. We have accomplished the efficient and asymmetric total synthesis of 1 in 16 steps from known compounds (20 steps from commercially available starting materials) by a modular synthetic strategy. A tetracyclic intermediate was prepared in a convergent manner through a Grignard reaction and a subsequent ring-closing metathesis reaction of two enantiomerically enriched fragments.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!