Sensing Remote Chirality: Stereochemical Determination of β-, γ-, and δ-Chiral Carboxylic Acids

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 β‐, γ‐, or δ‐chiral carboxylic acid t...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2015-03, Vol.54 (14), p.4274-4278
Main Authors: Tanasova, Marina, Anyika, Mercy, Borhan, Babak
Format: Article
Language:English
Subjects:
Binding
Carboxylic acids
Carboxylic Acids - chemistry
Chirality
circular dichroism
Complexation
Cotton
Helical
Helicity
host-guest systems
Models, Molecular
Stereochemistry
Stereoisomerism
Tasks
zinc
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 β‐, γ‐, or δ‐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. Binding of bis(porphyrin) tweezers to β‐, γ‐, or δ‐chiral carboxylic amides yields chiral helical complexes which generate a bisignate Cotton Effect (ECCD) to enable the unambiguous determination of the chirality for remote stereocenters. The sign of the observed ECCD curve can be related to the absolute stereochemistry of the bound chiral substrate in a predictable manner.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201410371