5-Carbaphosphatranes: the first main group atrane bearing a 1-5 covalent bond.
5-Carbaphosphatranes: the first main group atrane bearing a 1-5 covalent bond.
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5-碳磷酯：带有1-5个共价键的第一个主族莠烷。
DOI：
10.1021/ja0056264
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发表时间：
2001
影响因子：
15
通讯作者：
T. Kawashima
中科院分区：
文献类型：
--
作者：
J. Kobayashi;K. Goto;T. Kawashima
人们对各种各样的主群atranes进行了广泛的研究，通常描述为A。1迄今为止，还报道了它们的一些衍生物，它们具有不同的环尺寸和其他构建元素。这些研究表明，NfE配价键的性质对它们的结构和反应性有很大的影响。从这一观点出发，当5-氮原子和中心原子之间的配价键被如通式B所示的与14族元素如碳的共价键取代时，它们的性质将如何变化是特别令人感兴趣的。已知的氮杂三环化合物的5-位上的元素几乎仅限于氮，只有少数例外是磷。2本文报道了5-碳磷杂三环化合物1和2的合成，这是第一个主族氮杂三环化合物的5-碳类似物。虽然它们与通常的带有5-氮原子的磷杂三环具有等电子结构，但预期它们的反应性与通常的反应性相当不同，反映了1-5键性质的差异。
There have been extensive studies on a wide variety of main group atranes, generally depicted as A. 1 A number of their derivatives bearing different ring sizes and other building elements have also been reported so far. These studies established that the nature of the NfE dative bond has a great influence on their structures and reactivities. From such a viewpoint, it is particularly intriguing how their properties will change when the dative bond between the 5-nitrogen atom and the central atom is replaced by a covalent bond with a group 14 element like carbon as shown by a general formula B.However, there has been no example of such an atrane bearing a 1-5 covalent bond; the element at the 5-position of known atranes has been limited almost exclusively to nitrogen with a few exceptions of phosphorus. 2 Here we report the synthesis of 5-carbaphosphatranes 1 and 2, presenting the first example of 5-carbon analogues of main group atranes. While they have an isoelectronic structure with usual phosphatranes bearing a 5-nitrogen atom, they are expected to be quite different in reactivities from usual ones reflecting the differences in the properties of the 1-5 bond.