Dataset Information

A Phosphorus-Based Pacman Dication Generated by Cooperative Self-Activation of a Pacman Phosphane.

ABSTRACT: Formal coordination of phosphorus(III) by a calix[4]pyrrole Schiff base ligand was achieved through the reaction of this ligand with PCl₃ under basic conditions. The reaction product adopts a Pacman conformation with two P-Cl moieties, one in exo and one in endo position. It represents the first non-metal compound of calix[4]pyrrole Schiff base ligands and of Pacman ligands in general. The spatial neighborhood of the two phosphorus atoms enables cooperative reactions. As a first example, the chloride abstraction with AgOTf is presented, yielding a macrocyclic dication with two embedded phosphorus(III) monocations, which both undergo a cooperative, internal activation reaction with an adjacent C=N double bond. This intramolecular redox process affords two pentacoordinated phosphorus(V) centers within the Pacman dication. All reaction products were fully characterized and all results are supported by computations.

SUBMITTER: Eickhoff L

PROVIDER: S-EPMC9298836 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

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A Phosphorus-Based Pacman Dication Generated by Cooperative Self-Activation of a Pacman Phosphane.

Eickhoff Liesa L Ohms Leon L Bresien Jonas J Villinger Alexander A Michalik Dirk D Schulz Axel A

Chemistry (Weinheim an der Bergstrasse, Germany) 20211124 3

Formal coordination of phosphorus(III) by a calix[4]pyrrole Schiff base ligand was achieved through the reaction of this ligand with PCl<sub>3</sub> under basic conditions. The reaction product adopts a Pacman conformation with two P-Cl moieties, one in exo and one in endo position. It represents the first non-metal compound of calix[4]pyrrole Schiff base ligands and of Pacman ligands in general. The spatial neighborhood of the two phosphorus atoms enables cooperative reactions. As a first examp ...[more]

PMID: 34761445

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Project description:With the growing number and diversity of known genome sequences, there is an increasing opportunity to regulate gene expression through synthetic, cell-permeable small molecules. Enhancing the DNA sequence recognition abilities of minor groove compounds has the potential to broaden their therapeutic applications with significant implications for areas such as modulating transcription factor activity. While various classes of minor groove binding agents can selectively identify pure AT and mixed AT and GC base pair(s) containing sequences, there remains a lack of compounds capable of distinguishing between different AT sequences. In this work, we report on the design compounds that exhibit selective binding to -TTAA- or -TATA- containing DNA minor groove sequences compared with other AT ones. Several studies have shown that the -AATT- and -TTAA- sequences have distinct physical and interaction properties, especially in terms of their different requirements for recognition in the minor groove. Achieving strong, selective minor groove binding at -TTAA- sequences has been challenging, but DB1003, a benzimidazole-furan-furan diamidine, has demonstrated cooperative dimeric binding activity at -TTAA-. It has significantly less binding preference for AATT. To better understand and modify the selectivity, we synthesized a set of rationally designed analogs of DB1003 by altering the position of the five-membered heterocyclic structure. Binding affinities and stoichiometries obtained from biosensor-surface plasmon resonance experiments show that DB1992, a benzimidazolefuran-thiophene diamidine, binds strongly to -TTAA- as a positive cooperative dimer with high cooperativity. The high-resolution crystal structure of the TTAA-DNA-DB1992 complex reveals that DB1992 binds as an antiparallel π-stacked dimer with numerous diverse contacts to the DNA minor groove. This distinctive binding arrangement and the properties of diamidines at the -TTAA- minor groove demonstrate that benzimidazole-furan-thiophene is a unique DNA binding pharmacophore. Competition mass spectroscopy and circular dichroism studies confirmed the binding stoichiometry and selectivity preference of the compounds for the -TTAA- sequence.

Dataset Information

A Phosphorus-Based Pacman Dication Generated by Cooperative Self-Activation of a Pacman Phosphane.

Publications

A Phosphorus-Based Pacman Dication Generated by Cooperative Self-Activation of a Pacman Phosphane.

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