Synthesis of novel dihydroxydiphosphines and dihydroxydicarboxylic acids having a tetra(thio-1,3-phenylene-2-yl) backbone
Synthesis of novel dihydroxydiphosphines and dihydroxydicarboxylic acids having a tetra(thio-1,3-phenylene-2-yl) backbone
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具有四(硫代-1,3-亚苯基-2-基)主链的新型二羟基二膦和二羟基二羧酸的合成
DOI：
10.1080/10610278.2010.514913
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
and T. Hattori
中科院分区：
文献类型：
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作者：
Y. Akahira;K. Nagata;N. Morohashi;and T. Hattori
新型四齿PPh2-OH杂化配体5和CO2H-OH杂化配体6已由四(硫代-5-叔丁基-2-羟基-1,3-亚苯基)(24)成功合成，转化为双三氟甲磺酸酯后，用二苯基膦基或羧基取代2位和2′-、2″-或2‴位上的羟基基团8；新引入的取代基的取代位置在下文中用上标1,nas51,n表示。 Bistrilflates81,3 和 81,4 可以通过在不同条件下用四丁基氟化铵 (TBAF) 对 tetrakistriflate7 进行区域选择性去三氟甲基化来容易地制备。另一方面，bistriflate81,2的制备需要通过保护/去保护的四步过程。因此，四醇24与过量的1,3-二氯-1,1,3,3-四异丙基二硅氧烷的甲硅烷基化得到O,O'-和O'',O4-二硅氧烷-1,3-二基封端的衍生物9。通过用 0.5 摩尔当量的处理去除两个二硅氧烷桥之一。 TBAF 得到二醇10。二醇10的三氟甲磺酸酯化，然后除去剩余的二硅氧烷桥，得到双氟磺酸酯81,2。 Bistrilflates8经过钯催化的磷酸化，然后还原生成的氧化膦121，n得到PPh2–OH杂化配体51,n(n= 2–4)，而CO2H–OH杂化配体61,n(n= 3,4)是通过剩余羟基的乙酰化获得的，然后是钯催化的甲氧基羰基化TfO 部分，以及随后产生的四酯的水解14。二元酸61,3和61,4的X射线结构分析表明它们形成彼此完全不同的3D网络结构。有趣的是，61,4通过羧基之间分子间氢键形成的环状二聚体的堆叠，构建了一个具有作为超分子主体潜力的多孔通道。
Novel tetradentate PPh2–OH hybrid ligands5and CO2H–OH hybrid ligands6have been successfully synthesised from tetra(thio-5-tert-butyl-2-hydroxy-1,3-phenylene) (24) by replacing the hydroxy groups at both the 2-position and either the 2′-, 2″- or 2‴-position with diphenylphosphino or carboxy groups, after converting into bistriflates8; the substitution positions of newly introduced substituents are denoted hereafter by superscript 1,nas51,n. Bistriflates81,3and81,4can be readily prepared by the regioselective detriflation of tetrakistriflate7with tetrabutylammonium fluoride (TBAF), conducted under different conditions. On the other hand, the preparation of bistriflate81,2requires a four-step process through protection/deprotection. Thus, the silylation of tetraol24with an excess of 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane givesO,O′- andO″,O‴-disiloxane-1,3-diyl-capped derivative9. One of the two disiloxane bridges is removed by the treatment with 0.5 mol equiv. of TBAF to give diol10. Triflation of diol10, followed by the removal of the remaining disiloxane bridge, affords bistriflate81,2. Bistriflates8are subjected to palladium-catalysed phosphorylation, followed by the reduction of the resulting phosphine oxide121,nto give PPh2–OH hybrid ligands51,n(n= 2–4), while CO2H–OH hybrid ligands61,n(n= 3,4) are obtained from8via acetylation of the remaining hydroxy groups, followed by palladium-catalysed methoxycarbonylation of the TfO moieties, and subsequent hydrolysis of the resulting tetraesters14. X-ray structural analyses of dicarboxylic acids61,3and61,4reveal that they form quite different 3D network structures to each other. Interestingly,61,4constructs a porous channel with a potential for serving as a supramolecular host, by the stacking of its cyclic dimer that is formed by intermolecular hydrogen bondings between the carboxy groups.