Rapid Access to Chiral and Tripodal Cavitands from β-Pinene.
Rapid Access to Chiral and Tripodal Cavitands from β-Pinene.
复制标题
DOI：
10.1002/chem.202202416
复制
发表时间：
2022-12-27
影响因子：
4.3
通讯作者：
Badjic, Jovica D.
中科院分区：
文献类型：
--
作者：
Wang, Xiuze;Pavlovic, Radoslav Z.;Finnegan, Tyler J.;Karmakar, Pratik;Moore, Curtis E.;Badjic, Jovica D.
在这项工作中，我们报道了pd催化的(+)-α-溴烯酮的环三聚化反应，从单萜β -蒎烯中得到一个对映纯环三聚体。这个C3对称化合物有三个双环[3.1.1]庚烷环与中心苯相连，每个环上带有一个羰基。该环三聚体与5个末端炔的锂盐发生非对映选择性三烷基化反应（41-63%,de% = 4-83）。这个添加物使一个小的新型手性空腔库的快速合成成为可能，这些空腔的形状类似于三脚架。这些分子三脚架包括一个三-双环环连接的苯头，它与三个在一个方向上扭曲的炔脚相连，形成一个以极性基团为脚的非极性腔。甲基吡啶和甲基异喹啉三脚架分别与抗炎和手性药物(R)/(S)-布洛芬和(R)/(S)-萘普生形成包合物。结合模式表明，药物分子通过离子-离子、阳离子- π和C-H - π接触停靠在宿主的空腔中，除了溶解外，还产生了在水中具有mM至μM稳定性的配合物。我们的发现为创造无数具有可调功能的对不纯三脚架打开了大门，未来可能会产生新的化学传感器、催化剂或隔离剂。丰富的天然产物β -蒎烯可以迅速转化为手性宿主库，我们称之为分子三脚架。作为水中复杂手性药物的三脚架，它们有望发现和制造新的隔离剂、化学传感器或催化剂。研究所和/或研究员Twitter用户名：@BadjicL；@RadoslavPavlov4;@JBadjic
In this work, we report Pd-catalyzed cyclotrimerization of (+)-α-bromoenone, obtained from monoterpene β−pinene, into an enantiopure cyclotrimer. This C3 symmetric compound has three bicyclo[3.1.1]heptane rings fused to its central benzene with each ring carrying a carbonyl group. The cyclotrimer undergoes diastereoselective threefold alkynylation with lithium salts of five terminal alkynes (41–63%, de% = 4–83). The addition enabled a rapid synthesis of a small library of novel chiral cavitands that in shape resemble a tripod stand. These molecular tripods include a tris-bicycloannelated benzene head attached to three alkyne legs twisted in one direction to form a nonpolar cavity with polar groups as feet. Tripods with methylpyridinium and methylisoquinolinium legs, respectively, form inclusion complexes with anti-inflammatory and chiral drugs (R)/(S)-ibuprofen and (R)/(S)-naproxen. The mode of binding shows drug molecules docked in the cavity of the host via ion-ion, cation−π, and C-H−π contacts that, in addition of desolvation, give rise to complexes having mM to μM stability in water. Our findings open the door for creating a myriad of enantiopure tripods with tunable functions that, in the future, may give novel chemosensors, catalysts or sequestering agents. Abundant natural product β−pinene can be rapidly converted into a library of chiral hosts that we call molecular tripods. As tripods complex chiral drugs in water, they hold promise for discovering and building novel sequestering agents, chemosensors or catalysts. Institute and/or researcher Twitter usernames: @BadjicL; @RadoslavPavlov4; @JBadjic
登录
查看更多内容
影响因子：
62.1
作者：
Brill ZG;Condakes ML;Ting CP;Maimone TJ
通讯作者：
Maimone TJ
影响因子：
17.1
作者：
Das S;Nascimbeni G;de la Morena RO;Ishiwari F;Shoji Y;Fukushima T;Buck M;Zojer E;Zharnikov M
通讯作者：
Zharnikov M
DOI：
10.1002/advs.202004042
发表时间：
2021-04
期刊：
Advanced science (Weinheim, Baden-Wurttemberg, Germany)
影响因子：
--
作者：
Edelbrock AN;Clemons TD;Chin SM;Roan JJW;Bruckner EP;Álvarez Z;Edelbrock JF;Wek KS;Stupp SI
通讯作者：
Stupp SI
影响因子：
56.9
作者：
CRAM, DJ
通讯作者：
CRAM, DJ
影响因子：
56.9
作者：
CRAM, DJ
通讯作者：
CRAM, DJ