Design, Synthesis, and X‐ray Structural Analyses of Diamantane Diammonium Salts: Guests for Cucurbit[n]uril (CB[n]) Hosts
Design, Synthesis, and X‐ray Structural Analyses of Diamantane Diammonium Salts: Guests for Cucurbit[n]uril (CB[n]) Hosts
复制标题
金刚烷二铵盐的设计、合成和 X 射线结构分析：葫芦[n]脲 (CB[n]) 宿主的客体
DOI：
10.1002/ejoc.201301844
复制
发表时间：
2014
影响因子：
2.8
通讯作者：
K. Mlinarić
中科院分区：
文献类型：
--
作者：
Marina Šekutor;K. Molčanov;Liping Cao;L. Isaacs;R. Glaser;K. Mlinarić
合成了新的双伯和双季金刚烷-1，6-和-4，9-二铵/二胺盐，并用NMR和X-射线晶体学进行了表征。这些合成的动力是先前报道的金刚烷单和双季铵离子[3，5-diMeAda-1-NH3或Ada-1，3-di（NMe 3）]与葫芦[n]脲（n = 7，8）络合的X射线晶体学研究。晶体结构进行了分析，以确定可能的结构假设高结合亲和力的客人绑定在各种直径的南瓜形主机。虽然可以容易地从双伯前体制备Diam-4，9-二（NMe 3 I）5，但即使在强反应条件下也不能获得相应的Diam-1，6-二（NMe 3 I）14。这种情况的立体化学分析表明，非常严重的空间非键合顺式-1，3-二轴型H···H之间的相互作用的“轴”型NMe 3基团和相邻的“轴”质子邻居。在Ada-2，6-di（NMe 3 I）类似物中也发现了这些相同的相互作用，但是通过使轴向C（亚甲基）-NMe 3键倾斜远离其轴向邻居，这些相互作用在这种较小的多环骨架中得以减轻。然而，Diam-1，6-di（NMe 3 I）的类似结构释放是不可能的，因为其中的C（次甲基）-NMe 3键连接到金刚烷的刚性骨架上。
New bisprimary and bisquaternary diamantane-1,6- and -4,9-diammonium/diaminium salts were synthesized, and characterized by NMR spectroscopy and X-ray crystallography. The impetus for these syntheses were previously reported X-ray crystallographic investigations of adamantane mono- and bisquaternary ammonium ions [3,5-diMeAda-1-NH3 or Ada-1,3-di(NMe3)] complexed with cucurbit[n]uril (n = 7, 8). The crystal structures were analyzed to ascertain possible structural hypotheses for high binding affinity guests bound within various diameter pumpkin-shaped hosts. Although Diam-4,9-di(NMe3I) 5 could be readily prepared from the bisprimary precursor, corresponding Diam-1,6-di(NMe3I) 14 could not be obtained even under strong reaction conditions. Stereochemical analysis of this situation suggests very severe steric non-bonding cis-1,3-diaxial type H···H interactions between the “axial”-type NMe3 group and neighboring “axial” proton neighbors. These same interactions are found in Ada-2,6-di(NMe3I) analogues, but they are alleviated in this smaller polycyclic skeleton through tilting the axial C(methylene)–NMe3 bond away from its axial neighbors. However, similar structural relief for Diam-1,6-di(NMe3I) is not possible, because the C(methine)–NMe3 bond therein is ligated to the diamondoid's rigid skeleton.
影响因子：
1.8
作者：
H. F. Russell;J. Bremner;Jennifer Bushelle-Edghill;M. Lewis;Stacey R. Thomas;F. Bates
通讯作者：
H. F. Russell;J. Bremner;Jennifer Bushelle-Edghill;M. Lewis;Stacey R. Thomas;F. Bates
影响因子：
15
作者：
Liu, SM;Ruspic, C;Isaacs, L
通讯作者：
Isaacs, L