RuO4-catalyzed oxidative polycyclization of squalene.: Determination of the configuration of the penta-tetrahydrofuranyl diol product

被引：28
作者：
Caserta, T
Piccialli, V
Gomez-Paloma, L
Bifulco, G
机构：
[1] Univ Naples Federico II, Dipartimento Chim Organ & Biochim, I-80126 Naples, Italy
[2] Univ Salerno, Dipartimento Sci Farmaceut, I-84084 Fisciano, Salerno, Italy
来源：
TETRAHEDRON | 2005年 / 61卷 / 04期
关键词：
RuO4; squalene; oxidative polycyclization; penta-THF configuration; PCC; oxidative cleavage;
D O I：
10.1016/j.tet.2004.11.018
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The configuration of the penta-tetrahydrofuranyl diol (penta-THF) product obtained by a single-step, RuO4-catalyzed oxidative polycyclization of squalene, has been determined as cis-threo-cis-threo-trans-threo-trans-threo-trans. The cis-cis-trans-trans-trans sequence for the five contiguous THF rings has been established through extensive 2D-NMR spectroscopic studies carried out both on the intact molecule and on some of its derivatives, including the oxidative cleavage products obtained by degradation of the penta-THF with PCC/AcOH. Four different chemical approaches were devised to determine each of the four threo relationships within each carbon pair connecting adjacent THF rings in the molecule. To this aim, studies have been carried out either on some intermediates of the process leading to penta-THF, obtained by stopping the oxidation of squalene prior to completion, or on a degradation product of the penta-THF, obtained from the latter through a bidirectional double oxidative degradation with PCC. (C) 2004 Elsevier Ltd. All rights reserved.
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收藏
页码：927 / 939
页数：13
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