Development of novel molecular catalysts having tetraphenylphenyl unit

具有四苯基苯基单元的新型分子催化剂的开发

基本信息

批准号：
17550026
负责人：
TOKUNAGA Makoto
金额：
$ 2.3万
依托单位：
KYUSHU UNIVERCITY (2006)Hokkaido University (2005)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

项目摘要

We have elucidated that the function of ligands bearing tetraphenylphenyl group, which have rigid and spatially spread structure. The oxygen-, nitrogen-, and phosphorous-ligands having tetraphenylphenyl group were synthesized and were examined catalytic reactions using several kinds of metals. We aimed to find new reactions, high catalytic activity, and high selectivity compared to conventional catalysts. Indeed, in the last year we have explored the enhancement effect of stereoselectivity by the large asymmetric environment produced by tetraphenylphenyl group. The size of the tetraphenylphenyl group is approximately 1.3 nano meters. This is relatively larger than the ligands, which is used in usual homogeneous metal complex catalysts, however, smaller than supermolecular catalysts such as dendrimers. An advantage over the supermolecular catalysts is synthetic accessibility. In reality, we have examined asymmetric alcoholysis of vinyl ethers of 2,2'-dihydroxy-1.1'-biaryls and found tha … More t the diamine ligands bearing tetraphenylphenyl group exhibited higher performance : 1.3 times higher stereoselectivity and 2.0 times higher catalytic activity. This reaction is very useful because asymmetric synthesis of 2,2'-dihydroxy-1.1'-binaphtols is relatively easy but 2,2'-dihydroxy-1.1'-binphenols are not so easy. The reason is mainly due to the stability of radicals generating during the reaction. Therefore oxidative coupling of 2-naphtol is easy but phenol is difficult. We extended the research to the asymmetric synthesis of 2,2'-dihydroxy-1.1'-biaryls having phosphoryl and sulfonyl groups and succeeded kinetic resolution of these compounds in high selectivity. In addition, the compounds which have asymmetric center at phosphorous atom were examined to the reaction and found that kinetic resolution of these class of compounds can be carried out with high selectivities up to 39. Since asymmetric synthesis of these compounds are extremely difficult, the value of our reactions should be very high. Less

我们已经阐明了具有二苯基苯基的配体的功能，这些配体具有刚性和空间扩散的结构。合成了具有四苯基苯基的氧，氮和磷 - 并使用几种金属检查催化反应。与常规催化剂相比，我们旨在发现新的反应，高催化活性和高选择性。实际上，在去年，我们探讨了四苯基苯基产生的大型不对称环境的立体选择性增强效应。四苯基苯基的大小约为1.3纳米米。这比配体相对较大，该配体用于通常的近似金属复合催化剂，但是，它小于超分子催化剂，例如树突聚合物。比超分子催化剂的优势是合成可及性。实际上，我们检查了2,2'-二羟基-1.1'biaryls的乙烯基醚的不对称酒精中毒，并发现了……更多的二氨基配体含有二苯基苯基的二氨基配体暴露了更高的性能：1.3倍的立体选择性和更高的催化活性较高的2.0倍。该反应非常有用，因为2,2'-二羟基-1.1'-甲茶自的不对称合成相对容易，但是2,2'-二羟基-1.1.1'-苯酚并不容易。原因主要是由于反应过程中自由基产生的稳定性。因此，2-奈托尔的氧化耦合很容易，但苯酚很困难。我们将研究扩展到2,2'-二羟基-1.1'-biaryl具有磷酸和磺酰基基团的不对称合成，并在高选择性中成功地分解了这些化合物的动力学分辨率。此外，对反应检查了在磷原子上具有不对称中心的化合物，发现这些化合物的动力学分辨率可以用高达39的高选择性进行。由于这些化合物的不对称合成非常困难，因此我们反应的价值应该很高。较少的