Pseudorotaxanes with Self-Sorted Sequence and Stereochemical Orientation
Pseudorotaxanes with Self-Sorted Sequence and Stereochemical Orientation
复制标题
DOI：
10.1002/anie.201301570
复制
发表时间：
2013-07-15
影响因子：
16.6
通讯作者：
Neri, Placido
中科院分区：
文献类型：
--
作者：
Talotta, Carmen;Gaeta, Carmine;Neri, Placido
自分选是生命系统中的一个基本过程[1]，它控制生物分子复杂混合物的时空组织，[1a]如蛋白质，核酸，寡糖和脂质，成为大的功能组件（例如DNA双螺旋，[2a]多酶复合物，[1a]核糖体，[2b]或膜[1a]），并超越这些组件进入生命发展所必需的细胞隔室。[3]立体化学同质性[4]以及精确的结构单元序列-即序列异构性的精确控制-对于生物分子功能至关重要。例如，只有四个DNA碱基的序列定义了遗传密码。[2a受自然界的启发，合成超分子自分选系统[8，9]已经发展成为一个高兴趣的研究领域。像它们的天然类似物一样，它们选择性地从一个明显更大的可能的集合体中形成一个确定的和少量的超分子集合体。合成自分选系统的效率与其区分结构相似的个体亚基的能力有关。模仿自然系统的效率和复杂性的一个基本步骤是设计一个合成系统，该系统能够对在序列和立体化学水平上同时不同的物种进行分类。以前，我们报道了一种杂假[3]轮烷[10，11]，其具有两个相似的冠醚（二苯并[24]冠-8和苯并-[21]冠-7），它们以特定的顺序沿结构上不对称的二烷基铵轴沿着排列。[12]据我们所知，迄今为止，还没有一个系统的例子，在不同的物种之间的排序顺序和立体化学存在。最近，我们通过利用弱配位的[15 d，16] TFPB（四（3，5-三氟甲基）），[14] 1H或1 tBu（图1），在双（苄基烷基铵）轴（22+或32+）上螺旋，[15]合成了[13]假[3]轮烷。
Self-sorting is a fundamental process in living systems [1] which controls the spatiotemporal organization of complex mixtures of biomolecules,[1a] such as proteins, nucleic acids, oligosaccharides, and lipids, into large functional assemblies (eg the DNA double helix,[2a] multienzyme complexes,[1a] ribosomes,[2b] or membranes [1a]) and beyond these assemblies into cellular compartments essential for the development of life.[3] Stereochemical homogeneity [4] as well as precise buildingblock sequences—that is, accurate control of sequence isomerism—are pivotal for biomolecular function. For example, the sequence of only four DNA bases defines the genetic code.[2a, 5] Control of the stereochemical [6] and sequence [7] information by self-sorting is thus of prime importance for life.Inspired by nature, synthetic supramolecular self-sorting systems [8, 9] have developed into a high-interest research area. Like their natural analogues, they form selectively a defined and small number of supramolecular assemblies out of a significantly larger pool of possible assemblies. The efficiency of a synthetic self-sorting system is related to its ability to discriminate between structurally similar individual subunits. A fundamental step towards mimicking the efficiency and complexity of natural systems is to design a synthetic system able to sort species that simultaneously differ at the sequence and stereochemical levels. Previously, one of us reported a heteropseudo [3] rotaxane [10, 11] bearing two similar crown ethers (dibenzo [24] crown-8 and benzo-[21] crown-7) in a specific sequence along a constitutionally asymmetric dialkylammonium axle.[12] To the best of our knowledge, no examples of a system that sorts among species that differ in sequence and stereochemistry exist so far. Recently, we synthesized [13] pseudo [3] rotaxanes with calix [6] arenes,[14] 1H or 1tBu(Figure 1), threaded on a bis (benzylalkylammonium) axle, 22+ or 32+,[15] by exploiting the weakly coordinating [15d, 16] TFPB(tetrakis (3, 5-