Dynamic covalent chemistry

Stuart J. Rowan, Stuart J. Cantrill, Graham R L Cousins, Jeremy K M Sanders, J. Fraser Stoddart

Research output: Contribution to journalReview article

880 Citations (Scopus)

Abstract

Dynamic 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.

Original languageEnglish
Pages (from-to)899-952
Number of pages54
JournalAngewandte Chemie - International Edition
Volume41
Issue number6
Publication statusPublished - 2002 Mar 15
Externally publishedYes

Fingerprint

Self assembly
Catenanes
Rotaxanes
Supramolecular chemistry
Acetals
Covalent bonds
Isomers
Free energy
Capsules
Containers
Large scale systems
Chemical reactions
Esters
Polymers
Thermodynamics
Acids
Temperature

Keywords

  • Catenanes
  • Combinatorial chemistry
  • Macrocycles
  • Polymers
  • Rotaxanes
  • Supramolecular chemistry

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

Rowan, S. J., Cantrill, S. J., Cousins, G. R. L., Sanders, J. K. M., & Stoddart, J. F. (2002). Dynamic covalent chemistry. Angewandte Chemie - International Edition, 41(6), 899-952.

Dynamic covalent chemistry. / Rowan, Stuart J.; Cantrill, Stuart J.; Cousins, Graham R L; Sanders, Jeremy K M; Stoddart, J. Fraser.

In: Angewandte Chemie - International Edition, Vol. 41, No. 6, 15.03.2002, p. 899-952.

Research output: Contribution to journalReview article

Rowan, SJ, Cantrill, SJ, Cousins, GRL, Sanders, JKM & Stoddart, JF 2002, 'Dynamic covalent chemistry', Angewandte Chemie - International Edition, vol. 41, no. 6, pp. 899-952.
Rowan SJ, Cantrill SJ, Cousins GRL, Sanders JKM, Stoddart JF. Dynamic covalent chemistry. Angewandte Chemie - International Edition. 2002 Mar 15;41(6):899-952.
Rowan, Stuart J. ; Cantrill, Stuart J. ; Cousins, Graham R L ; Sanders, Jeremy K M ; Stoddart, J. Fraser. / Dynamic covalent chemistry. In: Angewandte Chemie - International Edition. 2002 ; Vol. 41, No. 6. pp. 899-952.
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