Automated Recognition, Sorting, and Covalent Self-Assembly by Predisposed Building Blocks in a Mixture

Rowan, Stuart J.; Hamilton, Darren G.; Brady, Paul A.; Sanders, Jeremy K. M.

doi:10.1021/ja963320k

Cited by 163 publications

(81 citation statements)

References 20 publications

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“…In the absence of copper(I), A, B, and C reacted to form a diverse dynamic library (16)(17)(18)(19) of product imines. ESI-MS indicated that this library included a variety of open-chain and macrocyclic products, the ligand of 3 being present only as a minority product.…”

Section: Resultsmentioning

confidence: 99%

“…Various templating (2-9) and self-recognition (10-15) phenomena have been used to shape the thermodynamics of different self-assembly processes, to select a desired product or products from a dynamic library (16)(17)(18)(19) of structures. Here we show how this goal may be accomplished through the action of a pair of metal template ions (20), which cooperatively direct each of the two equivalent aldehyde groups of a dialdehyde molecule to react with a different amine, forming two different imine (CAN) bonds selectively.…”

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confidence: 99%

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Synthetic selectivity through avoidance of valence frustration

Hutin

Bérnardinelli

Nitschke

2006

Proc. Natl. Acad. Sci. U.S.A.

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A series of di-copper(I) complexes has been prepared via the reaction of copper(I) tetrafluoroborate, 2,6-diformylpyridine, 8-aminoquinoline, and a series of aliphatic diamines and 4-substituted anilines. To avoid a ''valence-frustrated'' state, involving a mismatch between the number of ligand donor atoms and the number of metal acceptor sites, the product structures formed selectively: One of the formyl groups of the diformylpyridine reacted specifically with the aminoquinoline, whereas the other formyl group reacted with the diamine or aniline. The observed selectivity was demonstrated to be thermodynamic in nature: When two dicopper complexes that were stable yet ''valencefrustrated'' were mixed, an imine metathesis reaction was observed to occur spontaneously to generate a ''valence-satisfied'' structure. In addition to control over the constitution of the ligands, we were able to exercise control over their relative orientations within the complex. Diamines exclusively gave structures in which the ligand exhibited a head-to-head orientation along the copper-copper axis to avoid stretching. Anilines gave predominantly head-to-tail structures, with the proportion of head-to-head isomer decreasing in complexes that incorporate more electron-deficient anilines and disappearing in less polar solvents. We also demonstrated the removal of the metals and the hydrogenation of the imine bonds to generate a molecule containing nonexchanging secondary amines, suggesting potential uses of this technique in the domain of organic synthesis.coordination chemistry ͉ dynamic combinatorial chemistry ͉ synthesis ͉ self-assembly A challenging problem in chemical synthesis is the direction of two different reagents to react at two equivalent sites upon a single substrate molecule. When such a reaction is carried out under thermodynamic control (1), one may expect to generate mixtures of hetero-and homo-coupled products. This problem is compounded when one of the two reagents also possesses two reactive groups. Mixtures of oligomeric products are expected to form, as the difunctional starting materials combine to form polymeric chains and rings of different sizes (Eq. 1).Various templating (2-9) and self-recognition (10-15) phenomena have been used to shape the thermodynamics of different self-assembly processes, to select a desired product or products from a dynamic library (16-19) of structures. Here we show how this goal may be accomplished through the action of a pair of metal template ions (20), which cooperatively direct each of the two equivalent aldehyde groups of a dialdehyde molecule to react with a different amine, forming two different imine (CAN) bonds selectively. The self-assembly of this system was directed by means of the number of acceptor sites present on the Cu I template ions and the number of donor sites present on the self-assembled imine ligands. When the number of donor sites cannot readily equal the number of acceptor sites, a ''valence-frustrated'' or ''incommensurate'' (21) state results, providing a ...

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Synthetic selectivity through avoidance of valence frustration

Hutin

Bérnardinelli

Nitschke

2006

Proc. Natl. Acad. Sci. U.S.A.

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“…Sanders et al have reported examples of the thermodynamically controlled formation of select macrocycles containing complementary building blocks, as opposed to a multitude of theoretically possible compounds. [14] Some of the problems that may arise in practical applications of the targeted equilibrium shift in equilibrating pools are related to the presence of the target compound in the mixture. Indeed, one can envision a variety of side-interactions, of covalent or noncovalent types, that may interfere with the binding and equilibration processes.…”

Section: Resultsmentioning

confidence: 99%

“…The individual binding constants K of all the isomers were then determined from the changes in chemical shifts (Dd) of the host signals by nonlinear curve fitting to Equation (14) for the 1:1 complexation mode.…”

Section: Methodsmentioning

confidence: 99%

Use of Molecular Recognition To Drive Chemical Evolution: Mechanisms of an Automated Genetic Algorithm Implementation

Елисеев

Nelen

1998

Chem. Eur. J.

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A detailed description is provided for a new general approach that allows production of amplified amounts of effective noncovalent binders from pools of compounds that can exist in a dynamic equilibrium. This approach involves a) selective binding of the effective pool components by the immobilized target compound; b) equilibration of the pool remaining after selection, and thereby regeneration of the effective components; c) repetition of the selection ± equilibration cycles. It represents a new, automated, implementation of a genetic algorithm/mechanism in a chemical system. Application of the approach to the generation of arginine binders involved the synthesis and screening of eight compounds, each of which was capable of forming a pool of three isomers (trans,trans, trans,cis, and cis,cis) that could be interconverted by photoisomerization. These compounds were screened for their affinity for, or selectivity of binding to, guanidinium derivatives. The most promising compound was then used in our method to generate an amplified amount of the cis,cis isomer, the strongest binder from the equilibrating pool. The receptors were selected using an arginine derivative immobilized on the modified silica gel support, which had been found to possess binding affinity and selectivity similar to those of guanidinium salts in solution. Mathematical models of the approach were developed that allowed us to evaluate the importance of various experimental parameters and to assess the applicability of the method to larger combinatorial pools.

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“…We, and others [24][25][26][27][28][29][30][31][32][33][34][35], refer to such systems as self-sorting systems. For example, we selected 10 compounds from the literature well known to form supramolecular aggregates driven by H-bonding interactions and showed that this collection of aggregates forms even when all 10 components are mixed [36].…”

Section: Introductionmentioning

confidence: 99%

Deconvolution of a multi-component interaction network using systems chemistry

2010

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We describe the stepwise construction of an 8-component self-sorted system (1 -8) by the sequential addition of components. This process occurs via a large number of states (2 8 = 256) and even a larger number of pathways (8! = 40320). A pathway (5, 6, 7, 8, 4, 3, 2, then 1) that is self-sorted at every step along the way has been demonstrated experimentally. Another pathway (1,8,3,5,4,7, 2, then 6) resembles a game of musical chairs and exhibits interesting shuttling of guest molecules among hosts. The majority of pathways -unlike the special ones described above -proceed through several non self-sorted states. We characterized the remainder of the 40320 pathways by simulation using Gepasi and describe the influence of concentration and binding constants on the fidelity of the self-sorting pathways.

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Automated Recognition, Sorting, and Covalent Self-Assembly by Predisposed Building Blocks in a Mixture

Cited by 163 publications

References 20 publications

Synthetic selectivity through avoidance of valence frustration

Synthetic selectivity through avoidance of valence frustration

Use of Molecular Recognition To Drive Chemical Evolution: Mechanisms of an Automated Genetic Algorithm Implementation

Deconvolution of a multi-component interaction network using systems chemistry

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