Guanidinium Promoted
Cleavage of Phosphoric Diesters:
Kinetic Investigations and Calculations Provide Indications on the
Operating Mechanism
Version 2 2017-09-19, 12:54
Version 1 2017-09-19, 12:49
Posted on 2017-09-19 - 12:54
The catalytic activity
of the guanidinium units toward the cleavage
of phosphoric diesters is deeply investigated both with kinetic experiments
and DFT calculations. The first part of the investigation aims to
determine how the structure of the substrate (phenyl or alkyl esters)
is able to influence the guanidinium-catalyzed hydrolysis changing
the mechanism from ANDN to AN+DN. In the cleavage of the DNA model bis(4-nitrophenyl)phospate
(BNPP), experimental kinetic data highlight the operation of a guanidine–guanidinium
catalytic dyad that can act both intermolecularly and intramolecularly
on different molecular scaffolds exhibiting notable values of effective
molarity. 31P NMR spectra and DFT investigation provide
indication that the deprotonated guanidine involved in such a catalysis
acts as a general base in the deprotonation of a water molecule involved
in the cleavage, and not as nucleophilic unit. Moreover, DFT calculations
were carried out to determine the guanidinium promoted activation
energy of pseudorotation. The results indicate a remarkable drop in
the activation energy of this process for dialkylphosphate esters
explaining, in part, the higher sensitivity of diribonucleoside to
the presence of guanidinium-based catalysts compared to the more activated
RNA model HPNP.
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Salvio, Riccardo; Casnati, Alessandro (2017). Guanidinium Promoted
Cleavage of Phosphoric Diesters:
Kinetic Investigations and Calculations Provide Indications on the
Operating Mechanism. ACS Publications. Collection. https://doi.org/10.1021/acs.joc.7b01925
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