Stereochemical Determination of Five-Membered Cyclic Ether Acetogenins Using a Spin-Spin Coupling Constant Approach and DFT Calculations

Marine Drugs

Adrián Gutiérrez-Cepeda¹  Antonio Hernández Daranas¹  José J. Fernández¹  Manuel Norte¹ 

[1] University Institute of Bio-Organic Chemistry “Antonio González”, Center for Biomedical Research of the Canary Islands (CIBICAN), University of La Laguna, Astrofísico Francisco Sánchez 2, La Laguna 38206, Tenerife, Spain; E-Mails:

关键词: C₁₅ tetrahydrofuranyl-acetogenins;    marilzafurollenes;    marine natural products;    Laurencia;    five-membered rings;    J-based methodologies;    DFT calculations;   

DOI  :  10.3390/md12074031

来源: mdpi

【 摘 要 】

Five-membered rings are of particular interest, due to their presence in some of the most common molecules in chemistry and biology. Despite their apparent simplicity, the structural resolution of these rings is complex, due to their inherent conformational flexibility. Here, we describe an application of a recently reported simple and efficient NMR protocol based on the measurement of spin-spin coupling constants to achieve the challenging relative configurations of five new halogenated C₁₅ tetrahydrofuranyl-acetogenins, marilzafurollenes A–D (1–4) and 12-acetoxy-marilzafurenyne (5), isolated from the red alga, Laurencia marilzae. Although DFT chemical shift calculations were used to connect remote stereocenters, the NMR-based approach seems advantageous over computational techniques in this context, as the presence of halogens may interfere with reliable calculations.

【 授权许可】

CC BY   
© 2014 by the authors; licensee MDPI, Basel, Switzerland.