Monosubstituted derivatives of γ-cyclodextrin (γ-CD) are suitable building blocks for supramolecular polymers, and can also serve as precursors for the synthesis of other regioselectively monosubstituted γ-CD derivatives. We prepared a set of monosubstituted 2I-O-, 3I-O-, and 6I-O-(3-(naphthalen-2-yl)prop-2-en-1-yl) derivatives of γ-CD using two different methods. A key step of the first synthetic procedure is a cross-metathesis between previously described regioisomers of mono-O-allyl derivatives of γ-CD and 2-vinylnaphthalene which gives yields of about 16–25% (2–5% starting from γ-CD). To increase the overall yields, we have developed another method, based on a direct alkylation of γ-CD with 3-(naphthalen-2-yl)allyl chloride as the alkylating reagent. Highly regioselective reaction conditions, which differ for each regioisomer in a used base, gave the monosubstituted isomers in yields between 12–19%. Supramolecular properties of these derivatives were studied by DLS, ITC, NMR, and Cryo-TEM.
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机译：γ-环糊精（γ-CD）的单取代衍生物是超分子聚合物的合适结构单元，并且还可以用作合成其他区域选择性单取代γ-CD衍生物的前体。我们制备了一组单取代的2 I -O-，3 I -O-和6 I -O-（3-（萘使用两种不同的方法合成γ-CD的-2-yl）prop-2-en-1-yl）衍生物。第一个合成程序的关键步骤是在先前描述的γ-CD单-O-烯丙基衍生物与2-乙烯基萘的区域异构体之间进行交叉复分解，这可得到约16–25％（从γ-光盘）。为了提高总收率，我们开发了另一种方法，该方法基于以3-（萘-2-基）烯丙基氯为烷基化试剂的γ-CD直接烷基化。高度区域选择性的反应条件（在所用的碱中每种区域异构体均不同）使单取代的异构体的收率在12％至19％之间。通过DLS，ITC，NMR和Cryo-TEM研究了这些衍生物的超分子性质。
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