An iminoboronate construction set for subcomponent self-assembly
An iminoboronate construction set for subcomponent self-assembly
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DOI：
10.1002/chem.200800074
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发表时间：
2008-01-01
影响因子：
4.3
通讯作者：
Nitschke, Jonathan R.
中科院分区：
文献类型：
--
作者：
Hutin, Marie;Bernardinelli, Gerald;Nitschke, Jonathan R.
最近，我们已经证明了一系列的系统，其中复杂的结构，从简单的胺和醛的子组件铜（I）模板亚胺键形成。我们在本文中描述了这种“亚组分自组装”概念的扩展，以基于亚氨基硼酸酯基序产生结构。等摩尔量的二醇、胺和2-甲酰基苯基硼酸通过可逆的B-O和C=N键形成反应生成亚氨基硼酸酯，如James等人最近报道的（Org. Lett. 2006，8，609-612）。酯形成的程度取决于许多因素。对这些因素的探索使人们能够制定出控制自组装过程的规则和预测。这些规则允许构建包含多个硼原子的更复杂的结构，包括包含六个硼中心的三角笼，以及为构建更复杂的结构指明了方向。B-O和C=N键的不稳定性也允许不同的二醇和胺子组分在这些结构内被取代。选择规则也被确定为这些取代反应，允许的产品进行预测的基础上所采用的二醇和二胺的电子性质。因此，这些结果表明，通过其应用到一个新的动态共价体系的子组件自组装方法的一般性。
Recently we have demonstrated a series of systems in which complex structures were created from simple amine and aldehyde subcomponents by copper(I)-templated imine bond formation. We describe herein the extension of this "subcomponent self-assembly" concept to the generation of structures based upon the iminoboronate ester motif. Equimolar amounts of diol, amine, and 2-formylphenylboronic acid reacted by reversible B-O and C=N bond formation to generate iminoboronate esters, as has recently been reported by James et al. (Org. Lett. 2006, 8, 609-612). The extent of ester formation was shown to depend upon a number of factors. The exploration of these factors allowed rules and predictions to be formulated governing the self-assembly process. These rules allowed the construction of more complex structures containing multiple boron atoms, including a trigonal cage containing six boron centers, as well as pointing the way to the construction of yet more intricate architectures. The lability of the B-O and C=N bonds also allowed different diol and amine subcomponents to be substituted within these structures. Selection rules were also determined for these substitution reactions, allowing the products to be predicted based upon the electronic properties of the diols and diamines employed. These results thus demonstrate the generality of the subcomponent self-assembly methodology through its application to a new dynamic covalent system.