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

制备了末端带有肉桂醇部分的仲铵盐。以24元冠醚为原料合成了相应的拟轮烷化合物。末端封端反应由三丁基膦催化的酰化反应进行，得到末端含有大量肉桂酸酯基团的轮烷。以dppp为大分子配体，考察了钯配合物催化下的轮烷与大体积丙二酸烯丙酯的反应。以较高的产率合成了含丙二酸基的新型轮烷化合物。随着钯催化剂用量的减少，产率增加。当催化剂用量为5mol%时，端帽交换率达到95%。虽然轮烷中的氨基不干扰反应，但冠醚的空间位阻对反应有很强的抑制作用。反应继续进行而没有破坏联锁结构，因为由于…，车轴部件不能从车轴上穿出此外，在钯络合物形成过程中，钯催化剂上的大体积dppp配体激活了末端的肉桂酸酯基团。此外，利用酰胺基团之间的氢键作用，合成了具有环丁烯部分的轮烷，即掩蔽的1，3-二烯。当该轮烷在富马酸酯等亲二烯化合物的存在下加热时，环丁硫烯部分的分解和Diesl-Alder反应同时发生，得到一种新的具有环己烯基团的轮烷。这样得到的轮烷经臭氧氧化得到轮烷，其中轮烷的轴组分通过碳-碳双键的断裂而拉长。类似地，利用酰胺基团之间的氢键作用，合成了含有环丁硫烯和富马酸酯环的顺丁烯二烯。当加热顺丁烯二烯时，具有通过Diels-Alder聚合桥联的聚顺丁二烯结构的聚顺丁二烯。虽然这种聚合物具有桥联结构，但这是第一个具有多茂碳骨架的聚合物的例子。较少

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