Towards Stapling of Helical Alleno-Acetylene Oligomers - Synthesis of an Enantiopure Bis(ethynylvinylidene)-Substituted Cyclohexadeca-1,3,9,11-tetrayne
Towards Stapling of Helical Alleno-Acetylene Oligomers - Synthesis of an Enantiopure Bis(ethynylvinylidene)-Substituted Cyclohexadeca-1,3,9,11-tetrayne
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螺旋联烯乙炔低聚物的钉合 - 对映体纯双（乙炔基亚乙烯基）取代的环十六烷-1,3,9,11-四炔的合成
DOI：
10.1002/ejoc.201301529
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发表时间：
2014
影响因子：
2.8
通讯作者：
F. Diederich
中科院分区：
文献类型：
--
作者：
I.‐E. Sophie Müller;B. Bernet;Çağatay Dengiz;W. Schweizer;F. Diederich
我们感兴趣的是开发策略，以桥（“钉”）对映体纯的无环丙二烯-炔低聚物，以提高他们的构象偏好的螺旋二级结构，这被假定是在其特殊的手性性质的起源。我们发现，闭环复分解（RCM），这已被用于钉合肽螺旋，失败与非环状的烯属侧链装饰的丙二烯-乙炔二聚体。相反，发生烯炔RCM为对映体纯的二烯炔。我们切换到引入含二乙炔的桥梁，并在这里报告的15步合成的适度紧张，对映体纯的环己-1，3，9，11-四炔与氧化炔耦合的关键步骤。讨论了新化合物的手性性质。
We are interested in developing strategies to bridge (“staple”) enantiomerically pure acyclic alleno-acetylenic oligomers to enhance their conformational preferences for helical secondary structures, which are postulated to be at the origin of their exceptional chiroptical properties. We found that ring-closing metathesis (RCM), which has been used for the stapling of peptide helices, failed with an acyclic alleno-acetylene dimer decorated with lateral olefinic side chains. Instead, enyne RCM to an enantiomerically pure dienyne occurred. We switched to the introduction of diacetylene-containing bridges and report here the 15-step synthesis of a moderately strained, enantiomerically pure cyclohexa-1,3,9,11-tetrayne with an oxidative acetylenic coupling in the key step. The chiroptical properties of the new compounds are discussed.
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影响因子：
15
作者：
Spokoyny, Alexander M.;Zou, Yekui;Ling, Jingjing J.;Yu, Hongtao;Lin, Yu-Shan;Pentelute, Bradley L.
通讯作者：
Pentelute, Bradley L.
影响因子：
15
作者：
Kim, M;Miller, RL;Lee, DS
通讯作者：
Lee, DS
影响因子：
5.2
作者：
Stewart, Ian C.;Ung, Thay;Schrodi, Yann
通讯作者：
Schrodi, Yann
影响因子：
15
作者：
Yun, Sang Young;Kim, Mansuk;Lee, Daesung;Wink, Donald J.
通讯作者：
Wink, Donald J.