Molecular puzzle ring: pseudo[1]rotaxane from a flexible cyclodextrin derivative.
Molecular puzzle ring: pseudo[1]rotaxane from a flexible cyclodextrin derivative.
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DOI：
10.1021/ja806620z
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发表时间：
2008-11
影响因子：
15
通讯作者：
Atsuhisa Miyawaki;Paul Kuad;Y. Takashima;H. Yamaguchi;A. Harada
中科院分区：
文献类型：
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作者：
Atsuhisa Miyawaki;Paul Kuad;Y. Takashima;H. Yamaguchi;A. Harada
对端基较大的柔性环糊精(CD)衍生物(1-R)生成的拟[1]轮烷进行了动力学定量研究。1-R具有作为客体的肉桂酰胺部分和作为穿线过程的速率决定部分的大体积端基(R)。R基团对拟[1]轮烷的形成起着重要作用，R基团的大小和形状控制着自包结过程的动力学。分别具有金刚烷基和甲基端的1-Ad和1-Me衍生物通过穿透Altrose从(1)C(4)型到(4)C(1)型的构象转换的臂部分而形成自包合物。Altro-α-CD空腔的弹性导致诱导配位(从(1)C(4)到(4)C(1))到臂部分，并且引入一个大的末端基使这种拟[1]轮烷的稳定性得到提高。
A pseudo[1]rotaxane formed by a flexible cyclodextrin (CD) derivative (1-R) with a bulky end group has been investigated on kinetic quantitation. 1-Rs have the cinnamamide moiety as a guest and a bulky end group (R) as a rate-determining moiety of the threading process. The R groups play an important role for the formation of pseudo[1]rotaxane, and kinetics of the self-inclusion process was found to be controlled by the size and shapes of the R groups. 1-Ad and 1-Me derivatives, which have an adamantyl and methyl end group, respectively, formed self-inclusion complexes by threading of the arm moiety with a conformational conversion of altrose from (1)C(4) form to (4)C(1) form. Flexibility of the altro-alpha-CD cavity resulted in an induced fit (from (1)C(4) to (4)C(1)) to the arm moiety, and introducing a bulky end group allowed the stability of this pseudo[1]rotaxane to be enhanced.