Participation of alkoxy groups in reactions of acetals: violation of the reactivity/selectivity principle in a Curtin-Hammett kinetic scenario.
Participation of alkoxy groups in reactions of acetals: violation of the reactivity/selectivity principle in a Curtin-Hammett kinetic scenario.
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DOI：
10.1002/anie.201503525
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发表时间：
2015-10-05
期刊：
影响因子：
--
通讯作者：
Woerpel KA
中科院分区：
文献类型：
--
作者：
Garcia A;Sanzone JR;Woerpel KA
缩醛与距离四个碳原子的苄氧基的亲核取代反应可以是高度非对映选择性的。在一些情况下，选择性随着亲核试剂反应性的增加而增加，这违反了反应性-选择性原理。选择性随反应性的增加表明反应性中间体的多种构象异构体可以产生产物。
Nucleophilic substitution reactions of acetals with benzyloxy groups four carbon atoms away can be highly diastereoselective. The selectivity in several cases increased as the reactivity of the nucleophile increased, in violation of the reactivity-selectivity principle. The increase in selectivity with reactivity suggests that multiple conformational isomers of reactive intermediates can give rise to the products.