Chemically Fueled Transient Geometry Changes in Diphenic Acids

Transient changes in molecular geometry are key to the function of many important biochemical systems. Here, we show that diphenic acids undergo out-of-equilibrium changes in dihedral angle when reacted with a carbodiimide chemical fuel. Treatment of appropriately functionalized diphenic acids with...

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Bibliographic Details
Published in:Organic letters 2020-10, Vol.22 (19), p.7567-7571
Main Authors: Jayalath, Isuru M, Wang, Hehe, Mantel, Georgia, Kariyawasam, Lasith S, Hartley, C. Scott
Format: Article
Language:English
Subjects:
carbodiimides
chemical fuels
dissipative assembly
fuels
hydrolysis
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
mathematical methods
molecular machines
nuclear magnetic resonance spectroscopy
reaction products
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Summary:Transient changes in molecular geometry are key to the function of many important biochemical systems. Here, we show that diphenic acids undergo out-of-equilibrium changes in dihedral angle when reacted with a carbodiimide chemical fuel. Treatment of appropriately functionalized diphenic acids with EDC (N-(3-(dimethylamino)­propyl)-N′-ethylcarbodiimide hydrochloride) yields the corresponding diphenic anhydrides, reducing the torsional angle about the biaryl bond by ∼45°, regardless of substitution. In the absence of steric resistance, the reaction is well-described by a simple mechanism; the resulting kinetic parameters can be used to derive important properties of the system, such as yields and lifetimes. The reaction tolerates steric hindrance ortho to the biaryl bond, although the competing formation of (transient) byproducts complicates quantitative analysis.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.0c02757