Zirconocene-mediated, high-yielding macrocyclizations of silyl-terminated diynes.
Zirconocene-mediated, high-yielding macrocyclizations of silyl-terminated diynes.
复制标题
DOI：
10.1002/1521-3765(20020104)8:1
复制
发表时间：
2002-01
期刊：
影响因子：
--
通讯作者：
L. Schafer;J. Nitschke;S. Mao;Feng Liu;G. Harder;Markus Haufe;T. Tilley
中科院分区：
文献类型：
--
作者：
L. Schafer;J. Nitschke;S. Mao;Feng Liu;G. Harder;Markus Haufe;T. Tilley
合成了一系列不同长度和取代方式的硅基封端二炔化合物。这些二炔类化合物与直链炔类化合物选择性地形成三聚大环，而非线性二炔类化合物则生成环状二聚产物。为了制备具有大尺寸纳米空腔的大环，可以增加线性双炔的长度。含锆大环与酸反应生成不含金属的环番化合物。所有这些大环都是在没有高稀释条件的情况下以多克量制备的，从而使产品的产率达到75%，这些产品很容易提纯为结晶固体。
A series of silyl-terminated diynes of varying lengths and substitution patterns have been prepared. These diynes undergo zirconocene coupling with selective formation of trimeric macrocycles from linear alkynes, while nonlinear diynes give cyclodimeric products. The length of the linear diynes can be increased for the preparation of macrocycles with large nanoscale cavities. Reaction of the zirconium-containing macrocycles with acid results in the synthesis of metal-free cyclophanes. All of these macrocycles were prepared in multigram quantities, in the absence of high-dilution conditions, to give products in > 75% yield that are easily purified as crystalline solids.