Synthesis of (E)-1,2-diphosphanylethene derivatives from alkynes by radical addition of tetraorganodiphosphane generated in situ.
Synthesis of (E)-1,2-diphosphanylethene derivatives from alkynes by radical addition of tetraorganodiphosphane generated in situ.
复制标题
DOI：
10.1002/anie.200462603
复制
发表时间：
2005-03
影响因子：
--
通讯作者：
Akinori Sato;H. Yorimitsu;K. Oshima
中科院分区：
文献类型：
--
作者：
Akinori Sato;H. Yorimitsu;K. Oshima
有机磷化合物作为试剂、过渡金属的配体、生物活性物质和纳米结构的构建块，在有机化学中发挥着重要作用。其中，（E）-1，2-双（二苯基膦基）乙烯是近年来自组装领域的研究热点。[1]构建用作新功能材料的分级结构[2]需要具有官能团以诱导进一步组装的（E）-1，2-双（二苯基膦基）乙烯衍生物。然而，合成这种特殊的二膦基乙烯骨架的方法数量有限;这些合成总是在苛刻和/或强碱性条件下进行。[3]本文报道了一种以炔和四有机二膦为原料合成（E）-1，2-二（二苯基膦基）乙烯衍生物的方法。四有机二磷烷在C12 C三键上的自由基加成似乎是合成1，2-二磷烷基乙烯的直接策略。[4，5]然而，四有机二膦对氧如此敏感，以至于它们的制备、纯化和处理相当困难，必须在严格的惰性气氛下进行。[6]二膦在氧存在下的固有不稳定性在其合成应用中造成严重问题。本发明的二膦化反应采用在反应之前原位清洁地产生的四有机二膦。该方法的高效率将使合成的1，2-二膦基乙烯在有机材料科学中得到应用。
Organophosphorus compounds serve as reagents, ligands for transition metals, biologically active substances, and building blocks of nanoarchitectures, and thus play vital roles in organic chemistry. Among them,(E)-1, 2-bis (diphenylphosphanyl) ethene has recently attracted increasing attention in the field of self-assembly.[1] Construction of hierarchical structures for use as new functional materials [2] calls for derivatives of (E)-1, 2-bis (diphenylphosphanyl) ethene that have functional groups to induce further assembly. However, there are a limited number of methods for the synthesis of such peculiar diphosphanylethene skeletons; these syntheses are always carried out under harsh and/or strongly basic conditions.[3] Highly efficient and mild reactions affording (E)-1, 2-bis (diphenylphosphanyl) ethene derivatives are therefore required.Here we report a general, facile, and reliable synthesis of (E)-diphosphanylethene derivatives starting from an alkyne and a tetraorganodiphosphane. Radical addition of a tetraorganodiphosphane across a CÀC triple bond seems to be a straightforward strategy for the synthesis of 1, 2-diphosphanylethenes.[4, 5] However, tetraorganodiphosphanes are so sensitive to oxygen that their preparation, purification, and handling are quite difficult and must be carried out under a strictly inert atmosphere.[6] The inherent instability of diphosphanes in the presence of oxygen poses a serious problem in their synthetic use. The present diphosphanylation reaction employs a tetraorganodiphosphane that is cleanly generated in situ prior to the reaction. The high efficiency of this method will allow the 1, 2-diphosphanylethenes synthesized to be applicable in organic materials science.