Structural Reassignment, Absolute Configuration, and Conformation of Hypurticin, a Highly Flexible Polyacyloxy-6-heptenyl-5,6-dihydro-2H-pyran-2-one

被引：35

作者：

Alberto Mendoza-Espinoza, Jose ^{[2
,3
]}

Lopez-Vallejo, Fabian ^{[1
,2
,3
]}

Fragoso-Serrano, Mabel ^{[1
]}

Pereda-Miranda, Rogelio ^{[1
]}

Cerda-Garcia-Rojas, Carlos M. ^{[2
,3
]}

机构：

[1] Univ Nacl Autonoma Mexico, Fac Quim, Dept Farm, Mexico City 04510, DF, Mexico

[2] Inst Politecn Nacl, Ctr Invest & Estudios Avanzados, Dept Quim, Mexico City 07000, DF, Mexico

[3] Inst Politecn Nacl, Ctr Invest & Estudios Avanzados, Programa Posgrad Farmacol, Mexico City 07000, DF, Mexico

来源：

JOURNAL OF NATURAL PRODUCTS | 2009年 / 72卷 / 04期

关键词：

MOLECULAR-FORCE FIELD; ELECTRONIC CIRCULAR-DICHROISM; SPIN COUPLING-CONSTANTS; FUNCTIONAL THEORY CALCULATIONS; OPTICAL-ROTATION; STEREOSELECTIVE-SYNTHESIS; NATURAL-PRODUCTS; GEOMETRIES; STEREOCHEMISTRY; SPICIGEROLIDE;

D O I：

10.1021/np800447k

中图分类号：

Q94 [植物学];

学科分类号：

071001 [植物学];

摘要：

The structural reassignment, absolute configuration, and conformational behavior of the highly flexible natural product hypurticin (pectinolide E), 6S-[3'S,5'R,6'S-triacetoxy-1Z-heptenyl]-5S-acetoxy-5,6-dihydro-2H-pyran-2-one (1), were ascertained by a molecular modeling protocol, which includes extensive conformational searching, geometry optimization by DFT B3LYP/DGDZVP calculations, and comparison between the theoretical (DFT) and experimental H-1-H-1 NMR coupling constants. Hyptolide (2), a related cytotoxic 5,6-dihydro-2H-pyran-2-one that increased the S phase of the HeLa cell cycle, was employed as a reference substance to validate the theoretical protocol designed to characterize the 3D properties of compound 1. The related synthetic derivative, tri-O-acetyl-3,6-dideoxy-D-glucose diphenyldithioacetal (14), was prepared by a six-step reaction sequence starting from D-glucose and served as an enantiopure building block to reinforce the structural and configurational assignment of 1. This protocol proved to be an important tool for the structural characterization of highly flexible bioactive polyoxygenated natural products.

引用

页码：700 / 708

页数：9