Deracemization of a Dynamic Combinatorial Library Induced by (−)-Cytidine and (−)-2-Thiocytidine

Chung, Mee Kyung; Hebling, Christine M.; Jorgenson, James W.; Severin, Kay; Lee, Stephen J.; Gagné, Michel R.

doi:10.1021/ja803658n

Cited by 45 publications

(19 citation statements)

References 55 publications

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“…[6] The covalent argument is in accord with the molecular orbital description that two SOMOs overlap to form a bonding supermolecular orbital referring to a bonding electron pair in a covalent bond. [9,11,[15][16][17] This argument is illustrated in Figure 1 for the TCNE 2 2À anion radical dimer. The TCNE 2 2À dimer system is the smallest 2e-mc pancakebonded radical dimer and it serves well as a model system to understand pancake bonding.…”

Section: Introductionmentioning

confidence: 84%

Study of the Diradicaloid Character in a Prototypical Pancake‐Bonded Dimer: The Stacked Tetracyanoethylene (TCNE) Anion Dimer and the Neutral K₂TCNE₂ Complex

et al. 2013

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The π-bonded tetracyanoethylene anion dimer (TCNE2(2-)) and the neutral K2TCNE2 system have been investigated to obtain new insights into the unique features of two-electron multicenter (2e-mc) π-pancake bonding. The inter-radical interaction leads to a significant diradicaloid character described by two singly occupied molecular orbitals (SOMOs) of the monomers. A highly correlated approach, the multireference averaged quadratic coupled-cluster (MR-AQCC) method, has been used to achieve a balanced description of the different types of electron correlation that occur in this system. The analysis of the interaction energies for the two systems in the singlet and the lowest triplet states and of the unpaired electron densities demonstrate the importance of diradical π bonding in addition to the conventional van der Waals interactions that occur in intermolecular interactions. In this analysis, the separation of the repulsive Coulomb interaction energies from the remaining terms turned out to be a crucial prerequisite to achieve consistent results. Our calculations also confirm that the driving force behind the energetic stability of the pancake bonds predominantly derives from the overlap of the SOMO-SOMO bonding interaction.

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Section: Introductionmentioning

confidence: 84%

Study of the Diradicaloid Character in a Prototypical Pancake‐Bonded Dimer: The Stacked Tetracyanoethylene (TCNE) Anion Dimer and the Neutral K₂TCNE₂ Complex

et al. 2013

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“…A DCL formed by the racemic BB 38 rendered a mixture of cyclic oligomers of different sizes [37] and bearing all the possible stereochemical combinations of chiral centers. Thus, the corresponding derace mization of the mixture amplified two different macrocyclic pseudopeptides: the (S,S)-dimer from (−)-cytidine while the (R,R,R,R)-tetramer from (−)-2-thiocytidine [39]. The HPLC analysis coupled with a laser polarimeter detec tor and complementary studies with isotopically labeled pseudoenantiomers confirmed that the amplified dimer had (S,S) configuration [38].…”

Section: Pseudopeptides In Dynamic Covalent Chemistrymentioning

confidence: 83%

Non‐covalent Interactions for the Preparation of Pseudopeptidic Synthetic Compounds and Materials

Solà

Alfonso

2016

Non‐covalent Interactions in the Synthesis and Design of New Compounds

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“…LC -MS has been used by Gagn é et al in an elegant study showcasing some clever analytical chemistry for investigating chiral recognition in DCLs [11,12] . The authors screened a library made from a racemic hydrazide/aldehyde building block for binding to a chiral template using an optical rotation detector.…”

Section: Lc -Ms Analysismentioning

confidence: 99%

“…Application of DCLFit in experimental systems are now starting to appear [27,28] . For a smaller DCL a similar approach to determining binding constants has been reported making use of off -the -shelf software [12] .…”

Section: Quantifying Equilibrium Constantsmentioning

confidence: 99%

The Practice of Dynamic Combinatorial Libraries: Analytical Chemistry, Experimental Design, and Data Analysis

Otto

2010

Dynamic Combinatorial Chemistry

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IntroductionDynamic combinatorial chemistry ( DCC ) [1 -3] was originally developed to solve the problem of obtaining compounds with distinctive molecular recognition properties. These could be either ligands for biomolecules or synthetic receptors for small -molecule guests. Obtaining such molecules by a design -and -synthesis approach remains a daunting task; we simply do not suffi ciently understand issues like conformation and cooperation of the many individually weak noncovalent interactions that together determine effi ciency in molecular recognition. In DCC this problem is circumvented by limiting the design to only small fragments, which are assembled into the desired structures under the direction of the molecules themselves. A description of the basic principles of DCC is provided in Chapter 1 . Chapters 3 and 5 in this book provide ample proof that this approach indeed facilitates effi cient access to synthetic receptors and small -molecule ligands alike. The concept of DCC has also been explored in the context of catalyst development (Chapter 4 ) and polymer chemistry (Chapter 6 ).In many of these applications of DCC the purpose is to identify a specifi c molecule with exceptional properties. The dynamic combinatorial library ( DCL ) is then merely a vehicle through which this molecule may be generated and discovered. In a typical experiment a library is prepared by mixing building blocks, and its composition is analyzed in the absence and presence of an added template molecule or some other stimulus. Any compound in the mixture that is signifi cantly amplifi ed upon addition of the template should be a strong binder. This principle still drives much of the work in DCC, but is arguably rather simplistic. DCLs are complex mixtures of species that are interconnected through a set of equilibria and mass balances, and can behave in ways that are not always immediately intuitive, particularly when the focus is on the amplifi cation of individual molecules. In order to fully appreciate the behavior of a DCL it should be regarded in its entirety as a molecular network that strives to attain the lowest overall Gibbs energy. One of the implications is that the extent to which template binding and amplifi cation are correlated can vary, depending in part on how the experiments Dynamic Combinatorial Chemistry. Edited by Joost N. H. Reek and Sijbren Otto

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Deracemization of a Dynamic Combinatorial Library Induced by (−)-Cytidine and (−)-2-Thiocytidine

Cited by 45 publications

References 55 publications

Study of the Diradicaloid Character in a Prototypical Pancake‐Bonded Dimer: The Stacked Tetracyanoethylene (TCNE) Anion Dimer and the Neutral K₂TCNE₂ Complex

Study of the Diradicaloid Character in a Prototypical Pancake‐Bonded Dimer: The Stacked Tetracyanoethylene (TCNE) Anion Dimer and the Neutral K₂TCNE₂ Complex

Non‐covalent Interactions for the Preparation of Pseudopeptidic Synthetic Compounds and Materials

The Practice of Dynamic Combinatorial Libraries: Analytical Chemistry, Experimental Design, and Data Analysis

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Deracemization of a Dynamic Combinatorial Library Induced by (−)-Cytidine and (−)-2-Thiocytidine

Cited by 45 publications

References 55 publications

Study of the Diradicaloid Character in a Prototypical Pancake‐Bonded Dimer: The Stacked Tetracyanoethylene (TCNE) Anion Dimer and the Neutral K2TCNE2 Complex

Study of the Diradicaloid Character in a Prototypical Pancake‐Bonded Dimer: The Stacked Tetracyanoethylene (TCNE) Anion Dimer and the Neutral K2TCNE2 Complex

Non‐covalent Interactions for the Preparation of Pseudopeptidic Synthetic Compounds and Materials

The Practice of Dynamic Combinatorial Libraries: Analytical Chemistry, Experimental Design, and Data Analysis

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Product

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Study of the Diradicaloid Character in a Prototypical Pancake‐Bonded Dimer: The Stacked Tetracyanoethylene (TCNE) Anion Dimer and the Neutral K₂TCNE₂ Complex

Study of the Diradicaloid Character in a Prototypical Pancake‐Bonded Dimer: The Stacked Tetracyanoethylene (TCNE) Anion Dimer and the Neutral K₂TCNE₂ Complex