Ynamide carbopalladation: a flexible route to mono-, bi- and tricyclic azacycles.
Ynamide carbopalladation: a flexible route to mono-, bi- and tricyclic azacycles.
复制标题
DOI：
10.1002/chem.201501710
复制
发表时间：
2015-09-01
期刊：
影响因子：
--
通讯作者：
Anderson EA
中科院分区：
文献类型：
--
作者：
Campbell CD;Greenaway RL;Holton OT;Walker PR;Chapman HA;Russell CA;Carr G;Thomson AL;Anderson EA
溴基酰胺是氮杂环多样性的前体，通过碳环化的级联序列，然后是交叉偶联/电环化或还原过程。披露了我们对分子内酰胺碳中和研究的全部细节，其中包括使用有机三氟硼酸钾进行碳中和/交叉偶联反应的第一个例子；并了解影响这些过程成功的因素，包括环尺寸和耦合伙伴的性质。其他的机理观察也被报道，例如分离出用于电环化的三烯中间体。本文还描述了利用产物杂环的各种杂环- Diels-Alder反应，为Diels-Alder区域选择性的研究提供了新的思路。
Bromoenynamides represent precursors to a diversity of azacycles by a cascade sequence of carbopalladation followed by cross-coupling/electrocyclization, or reduction processes. Full details of our investigations into intramolecular ynamide carbopalladation are disclosed, which include the first examples of carbopalladation/cross-coupling reactions using potassium organotrifluoroborate salts; and an understanding of factors influencing the success of these processes, including ring size, and the nature of the coupling partner. Additional mechanistic observations are reported, such as the isolation of triene intermediates for electrocyclization. A variety of hetero-Diels–Alder reactions using the product heterocycles are also described, which provide insight into Diels–Alder regioselectivity.