A Substrate-Based Approach to Skeletal Diversity from Dicobalt Hexacarbonyl (C1)-Alkynyl Glycals by Exploiting Its Combined Ferrier-Nicholas Reactivity

被引：16

作者：

Lobo, Fernando ^{[1
]}

Gomez, Ana M. ^{[1
]}

Miranda, Silvia ^{[1
]}

Cristobal Lopez, J. ^{[1
]}

机构：

[1] CSIC, Inst Quim Organ Gen, Dept Bioorgan Chem, E-28006 Madrid, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2014年 / 20卷 / 33期

关键词：

Ferrier reaction; glycals; Nicholas reaction; synthesis design; synthetic methods; PAUSON-KHAND REACTIONS; STEREOSELECTIVE-SYNTHESIS; ORIENTED SYNTHESIS; PRINS REACTION; 1,4-ASYMMETRIC INDUCTION; INTRAMOLECULAR NICHOLAS; C-GLYCOSYLATION; ACID; CATIONS; LEWIS;

D O I：

10.1002/chem.201402149

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Novel substrates that combine dicobalt hexacarbonyl propargyl (Nicholas) and pyranose-derived allylic (Ferrier) cations have been generated by treatment of hexacarbonyldicobalt (C-1)-alkynyl glycals with (BF3Et2O)-Et-.. The study of these cations has resulted in the discovery of novel reaction pathways that have shown to be associated to the nature of O-6 substituent in the starting alkynyl glycals. Accordingly, compounds resulting from ring expansion (oxepanes), ring contraction (tetrahydrofurans), or branched pyranoses, by incorporation of nucleophiles, can be obtained from 6-O-benzyl, 6-hydroxy, or 6-O-silyl derivatives, respectively. The use of a 6-O-allyl alkynyl glycal led to a suitable funtionalized oxepane able to experience an intramolecular Pauson-Khand cyclization leading to a single tricyclic derivative.

引用

页码：10492 / 10502

页数：11