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

制备了在末端具有肉桂醇部分的仲铵盐。用24元冠醚合成了相应的准轮烷。以三丁基膦为催化剂，通过酰化反应进行封端反应，得到了末端含有庞大肉桂酯基的轮烷。以dppp为大体积配体，研究了钯配合物催化轮烷与大体积烯丙基丙二酸酯的反应。以良好的产率获得了具有丙二酸酯基团的新轮烷。产率随着钯催化剂的量减少而增加。当使用5mol%的催化剂时，实现了95%的封端交换。虽然轮烷中的铵基不干扰反应，但反应被冠醚的空间位阻强烈抑制。反应在不破坏互锁结构的情况下进行，因为轴部件由于以下原因而不能从轴旋出： ...更多信息 在钯络合期间钯催化剂上的大体积DPPP配体活化了末端肉桂酸酯基。此外，使用酰胺基团之间的氢键相互作用制备具有作为掩蔽的1，3-二烯的环丁烯砜部分的轮烷。在富马酸酯等亲二烯体存在下加热该轮烷时，同时发生环丁烯砜部分的分解和Diesl-Alder反应，得到具有环己烯基的新轮烷。臭氧氧化由此得到的轮烷提供了轮烷，其中轴组件被延长的裂解的碳-碳双键。使用酰胺基团之间的氢键相互作用类似地制备包含含亚砜环和含富马酸酯环的索烃。在加热该链烷烃时，通过Diels-Alder聚合反应生成具有桥连聚链烷烃结构的聚链烷烃。虽然该聚合物具有桥接结构，但这是具有聚链烷骨架的聚合物的第一个实例。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