Direct kinetic formation of nonanomeric [6.5]-spiroketals in aqueous media

被引:11
作者
Castagnolo, Daniele [1 ]
Breuer, Irene [1 ]
Pihko, Petri M. [1 ]
机构
[1] Aalto Univ, Organ Chem Lab, FI-02015 Espoo, Finland
关键词
D O I
10.1021/jo702022u
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The direct kinetic formation of spiroketals from mixed ketal-alcohol precursors under acid catalysis was studied using four differently substituted systems. In all cases, the exclusive formation of the anomeric isomer was observed under equilibrating conditions. However, the formation of the nonanomeric spiroketal isomer was observed if the reaction was performed under kinetic conditions using an appropriately tuned acid. Water had a dramatic accelerating effect on the spiroketalization reactions that were performed in THF, and the highest yields of the nonanomeric products were obtained in aqueous THE The nonanomeric/anomeric product ratio was also strongly affected by the substituents and the stereochemistry of the starting alcohol.
引用
收藏
页码:10081 / 10087
页数:7
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