Sensing Remote Chirality: Stereochemical Determination of β-, γ-, and δ-Chiral Carboxylic Acids
Sensing Remote Chirality: Stereochemical Determination of β-, γ-, and δ-Chiral Carboxylic Acids
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DOI：
10.1002/anie.201410371
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发表时间：
2015-03-27
影响因子：
16.6
通讯作者：
Borhan, Babak
中科院分区：
文献类型：
--
作者：
Tanasova, Marina;Anyika, Mercy;Borhan, Babak
确定具有远程非官能化立体中心的小分子的绝对立体化学是一项具有挑战性的任务。提出了一种使用适当取代的双（卟啉）镊子的解决方案。适当衍生的β-、γ-或δ-手性羧酸与镊子的络合诱导双（卟啉）的可预测螺旋度，其被检测为双信号棉花效应（ECCD）。ECCD曲线的符号与基于导出的工作助记符的底物的绝对立体化学以可预测的方式相关。
Determining the absolute stereochemisty of small molecules bearing remote nonfunctionalizable stereocenters is a challenging task. Presented is a solution in which appropriately substituted bis(porphyrin) tweezers are used. Complexation of a suitably derivatized beta-, gamma-, or delta-chiral carboxylic acid to the tweezer induces a predictable helicity of the bis(porphyrin), which is detected as a bisignate Cotton Effect (ECCD). The sign of the ECCD curve is correlated with the absolute stereochemistry of the substrate based on the derived working mnemonics in a predictable manner.