C–C Bond-Forming and Bond-Breaking Processes from the Reaction of Diesters with Me<sub>3</sub>SnLi. Synthesis of Complex Bridged Polycycles and Dialkyl Aromatic Compounds
作者:Lucas Martínez-García、Rubén Lobato、Gustavo Prado、Pablo Monje、F. Javier Sardina、M. Rita Paleo
DOI:10.1021/acs.joc.8b02891
日期:2019.2.15
followed by a reaction of the resulting unsaturated diesters with Me3SnLi. We propose that a stanna-Brook rearrangement plays a fundamental role in the formation of the polycyclic organotin acetals obtained. These unusual compounds could be further functionalized by tin–lithium exchange followed by alkylation of the newly formed tertiary carbanion. Alternatively, dialkylated aromatic hydrocarbons have
1,2-芳族二酯可以通过两步程序转变为应变桥联多环结构,该程序包括由碱金属促进的初始还原烷基化,然后使所得的不饱和二酯与Me 3 SnLi反应。我们提出,斯坦纳-布鲁克重排在获得的多环有机锡缩醛的形成中起基本作用。这些不寻常的化合物可以通过锡-锂交换,然后对新形成的叔碳负离子进行烷基化来进一步功能化。或者,已经通过Me 3 SnLi促进的脱碳反应制备了二烷基化的芳族烃。1,4-芳族二酯经过还原二烷基化,然后通过与Me 3反应转化为降冰片二烯酮衍生物SnLi。从蒽38开始,仅用两步就制备了几种稳定的二苯并降冰片二烯酮41。相应的萘类似物得到1,4-二烷基萘。所描述的合成协议提供对通过现有合成方法不容易获得的结构的访问。