File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Dynamic covalent chemistry

TitleDynamic covalent chemistry
Authors
KeywordsCatenanes
Combinatorial chemistry
Macrocycles
Polymers
Rotaxanes
Supramolecular chemistry
Issue Date2002
Citation
Angewandte Chemie - International Edition, 2002, v. 41, n. 6, p. 898-952 How to Cite?
AbstractDynamic covalent chemistry relates to chemical reactions carried out reversibly under conditions of equilibrium control. The reversible nature of the reactions introduces the prospects of "error checking" and "proof-reading" into synthetic processes where dynamic covalent chemistry operates. Since the formation of products occurs under thermodynamic control, product distributions depend only on the relative stabilities of the final products. In kinetically controlled reactions, how- ever, it is the free energy differences between the transition states leading to the products that determines their relative proportions. Supramolecular chemistry has had a huge impact on synthesis at two levels: one is non-covalent synthesis, or strict self-assembly, and the other is supramolecular assistance to molecular synthesis, also referred to as self-assembly followed by covalent modification. Noncovalent synthesis has given us access to finite supermolecules and infinite supramolecular arrays. Supramolecular assistance to covalent synthesis has been exploited in the construction of more-complex systems, such as interlocked molecular compounds (for example, catenanes and rotaxanes) as well as container molecules (molecular capsules). The appealing prospect of also synthesizing these types of compounds with complex molecular architectures using reversible covalent bond forming chemistry has led to the development of dynamic covalent chemistry. Historically, dynamic covalent chemistry has played a central role in the development of conformational analysis by opening up the possibility to be able to equilibrate configurational isomers, sometimes with base (for example, esters) and sometimes with acid (for example, acetals). These stereochemical "balancing acts" revealed another major advantage that dynamic covalent chemistry offers the chemist, which is not so easily accessible in the kinetically controlled regime: the ability to re-adjust the product distribution of a reaction, even once the initial products have been formed, by changing the reaction's environment (for example, concentration, temperature, presence or absence of a template). This highly transparent, yet tremendously subtle, characteristic of dynamic covalent chemistry has led to key discoveries in polymer chemistry. In this review, some recent examples where dynamic covalent chemistry has been demonstrated are shown to emphasise the basic concepts of this area of science.
Persistent Identifierhttp://hdl.handle.net/10722/332275
ISSN
2023 Impact Factor: 16.1
2023 SCImago Journal Rankings: 5.300
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorRowan, Stuart J.-
dc.contributor.authorCantrill, Stuart J.-
dc.contributor.authorCousins, Graham R.L.-
dc.contributor.authorSanders, Jeremy K.M.-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:10:12Z-
dc.date.available2023-10-06T05:10:12Z-
dc.date.issued2002-
dc.identifier.citationAngewandte Chemie - International Edition, 2002, v. 41, n. 6, p. 898-952-
dc.identifier.issn1433-7851-
dc.identifier.urihttp://hdl.handle.net/10722/332275-
dc.description.abstractDynamic covalent chemistry relates to chemical reactions carried out reversibly under conditions of equilibrium control. The reversible nature of the reactions introduces the prospects of "error checking" and "proof-reading" into synthetic processes where dynamic covalent chemistry operates. Since the formation of products occurs under thermodynamic control, product distributions depend only on the relative stabilities of the final products. In kinetically controlled reactions, how- ever, it is the free energy differences between the transition states leading to the products that determines their relative proportions. Supramolecular chemistry has had a huge impact on synthesis at two levels: one is non-covalent synthesis, or strict self-assembly, and the other is supramolecular assistance to molecular synthesis, also referred to as self-assembly followed by covalent modification. Noncovalent synthesis has given us access to finite supermolecules and infinite supramolecular arrays. Supramolecular assistance to covalent synthesis has been exploited in the construction of more-complex systems, such as interlocked molecular compounds (for example, catenanes and rotaxanes) as well as container molecules (molecular capsules). The appealing prospect of also synthesizing these types of compounds with complex molecular architectures using reversible covalent bond forming chemistry has led to the development of dynamic covalent chemistry. Historically, dynamic covalent chemistry has played a central role in the development of conformational analysis by opening up the possibility to be able to equilibrate configurational isomers, sometimes with base (for example, esters) and sometimes with acid (for example, acetals). These stereochemical "balancing acts" revealed another major advantage that dynamic covalent chemistry offers the chemist, which is not so easily accessible in the kinetically controlled regime: the ability to re-adjust the product distribution of a reaction, even once the initial products have been formed, by changing the reaction's environment (for example, concentration, temperature, presence or absence of a template). This highly transparent, yet tremendously subtle, characteristic of dynamic covalent chemistry has led to key discoveries in polymer chemistry. In this review, some recent examples where dynamic covalent chemistry has been demonstrated are shown to emphasise the basic concepts of this area of science.-
dc.languageeng-
dc.relation.ispartofAngewandte Chemie - International Edition-
dc.subjectCatenanes-
dc.subjectCombinatorial chemistry-
dc.subjectMacrocycles-
dc.subjectPolymers-
dc.subjectRotaxanes-
dc.subjectSupramolecular chemistry-
dc.titleDynamic covalent chemistry-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/1521-3773(20020315)41:6<898::aid-anie898>3.0.co;2-e-
dc.identifier.pmid12491278-
dc.identifier.scopuseid_2-s2.0-0000671730-
dc.identifier.volume41-
dc.identifier.issue6-
dc.identifier.spage898-
dc.identifier.epage952-
dc.identifier.isiWOS:000174450300001-

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats