Improvement of the performance of interlocked compounds by the selective modification of their structure

通过选择性修饰联锁化合物的结构来提高其性能

基本信息

批准号：
15550128
负责人：
KIHARA Nobuhiro
金额：
$ 2.24万
依托单位：
Osaka Prefecture University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

Secondary ammonium salts having cinnamyl alcohol moiety at the termini were prepared. Corresponding pseudorotaxanes were prepared with 24-membered crown ether. The end-capping reaction was carried out by the acylation reaction catalyzed by tributylphosphane to afford rotaxanes having bulky cinnamyl ester group at the termini. The reaction of thus obtained rotaxanes with bulky allylmalonate ester catalyzed by the palladium complexes was investigated using dppp as the bulky ligand. The new rotaxanes having malonate group was obtained in good yield. The yield increased as the amount of the palladium catalyst decreased. When 5 mol% of the catalyst was used, 95% of end-cap-exchange was achieved. Although the ammonium group in the rotaxane did not disturb the reaction, the reaction was strongly suppressed by the steric hindrance of the crown ether. The reaction proceeded without the destruction of the interlocked structure because the axle component could not thread out from the axle due to … More the bulky dppp ligand on the palladium catalyst during the palladium complex activated the terminal cinnamate ester group. Further, a rotaxane having sulfolene moiety that is the masked 1,3-diene was prepared using the hydrogen-bonding interaction between amide groups. When this rotaxane was heated in the presence of dienophile such as fumalate ester, the decomposition of sulfolene moiety followed by the Diesl-Alder reaction simultaneously occurred to afford a new rotaxane having cyclohexene group. Ozone oxidation of thus obtained rotaxane afforded the rotaxane in which the axle component was elongated by the cleavage of the carbon-carbon double bond. A catenane comprising sulfolene-containing ring and fumalate ester-containing ring was similarly prepared using the hydrogen-bonding interaction between amide groups. Upon heating the catenane, a polycatenane having bridged polycatenane structure by the Diels-Alder polymerization. Although this polymer has bridged structure, this is the first example of the polymer having polycatenane skeleton. Less

在末端准备了肉桂醇部分的次要铵销售。用24元的皇冠醚制备相应的伪tha菜。末端限制反应是通过托物磷酸催化的酰基反应进行的，可在末端提供具有笨重的肉桂基酯基的旋转烷。因此，使用DPPP作为笨重的配体研究了这样获得的轮济与由钯络合物催化的笨重的烯丙基酯酯的反应。具有丙二酸酯基团的新旋转烷的产量良好。随着钯催化剂的量减少，产量增加。当使用5摩尔％的催化剂时，实现了95％的端盖 - 交换。尽管轮济烷中的铵基并没有干扰反应，但反应被冠状以太的空间障碍强烈抑制。该反应在没有破坏互锁结构的情况下进行，因为轴成分无法从车轴上螺纹，这是因为……钯络合物期间钯催化剂上的较大DPPP配体激活了末端肉桂酯组。此外，使用酰胺基组之间的氢键相互作用制备了具有磺酰烯部分的轮济烷。当这种轮济烷在存在二热酯（例如烟酸酯）的情况下加热时，同样发生了磺胺部分部分的分解，然后是diesl-alder反应的分解，以提供具有环己烯基团的新的Rotaxane。因此获得的轮济烷的臭氧氧化提供了轮济，其中轴成分通过碳碳双键的裂解拉长。同样，使用酰胺基之间的氢键相互作用，制备了完成含氧环和富含烟酸酯的环的蛋白酸环烯烷和富富酸酯环。加热后，蛋白烷烷，一种由Diels-Alder聚合化的聚元烯烷，具有桥接多产素的结构。尽管该聚合物具有桥接结构，但这是具有多产素骨架的聚合物的第一个例子。较少的

项目成果

期刊论文数量（37）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Asymmetric Benzoin Condensation Catalyzed by Chiral Rotaxanes Tethering Thiazolium Salt Moiety via The Cooperation of The Component

手性轮烷通过组分配合束缚噻唑鎓盐部分催化不对称安息香缩合

DOI：
发表时间：
2004
期刊：
J.Am.Chem.Soc. 126・11
影响因子：
0
作者：
Atula S.D.Sandanayaka et al.;Nobuhiro Kihara et al.;Nobuhiro Watanabe et al.;Nobuhiro Kihara et al.;Nobuhiro Watanabe et al.;Yuya Tachibana et al.;Yuya Tachibana et al.
通讯作者：
Yuya Tachibana et al.

Redox Behavior of Ferrocene-Containing Rotaxane : Transposition of the Rotaxane Wheel by Redox Reaction of a Ferrocene Moiety

含二茂铁的轮烷的氧化还原行为：通过二茂铁部分的氧化还原反应进行轮烷轮的转位

DOI：
发表时间：
2004
期刊：
Org Lett. 6・11
影响因子：
0
作者：
Nobuhiro Kihara;et al.
通讯作者：
et al.

End-capping of a Pseudorotaxane via Diets-Alder Reaction for the Construction of C60-Terminated [2]Rotaxanes

通过 Diets-Alder 反应对拟轮烷进行封端以构建 C60 封端的 [2] 轮烷

DOI：
发表时间：
2004
期刊：
Org Lett. 6・22
影响因子：
0
作者：
M.Mitsui;S.Nagaoka;T.Matsumoto;A.Nakajima;H.Nishikawa et al.;Hisahiro Sasabe et al.
通讯作者：
Hisahiro Sasabe et al.

End-cap exchange of rotaxane by the Tsuji-Trost allylation reaction