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Advances in the catalyst- and reagent-controlled site-divergent intermolecular functionalization of C(sp3)–H bonds

  • Alexander Fawcett

    Alexander Fawcett completed his MSci in Chemistry at the University of Birmingham, UK, in 2014. He then moved to the University of Bristol, UK, where he completed his Ph.D. under the supervision of Professor Varinder K. Aggarwal in 2018. Here, he developed new methods for the preparation of organoboron compounds and investigated the reactivity of novel strained boronate complexes. For this work, he was awarded the 2019 IUPAC-Solvay International Award for Young Chemists and was a finalist for the Reaxys Ph.D. Prize 2019. In late 2018, he moved to the University of California, Berkeley, where he is currently working as a postdoctoral researcher under the supervision of Professor John F. Hartwig on the mechanistically-driven design and development of highly site selective C(sp3)–H bond functionalization reactions and applying them to the late-stage functionalization of complex molecules.

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Published/Copyright: September 28, 2020
Pure and Applied Chemistry
From the journal Pure and Applied Chemistry Volume 92 Issue 12

Abstract

Intermolecular C(sp3)–H bond functionalization reactions promise to revolutionize how we synthesize organic molecules by enabling the introduction of functionality at previously inert sites. However, one of the greatest challenges in this research field is site-selectivity, wherein chosen C(sp3)–H bonds must be selectively functionalized and other C(sp3)–H bonds with similar stereoelectronic properties must remain intact. To address this problem, chemists have developed methods that rely on targeting innately more reactive C(sp3)–H bonds or on using pre-installed functional groups to direct a catalyst or reagent to a particular C(sp3)–H bond. However, such approaches invariably have limited applicability because only a handful of innately reactive C(sp3)–H bonds or those nearby certain functional groups can be functionalized with good site-selectivity. To overcome these limitations, chemists also have developed catalysts and reagents that control the site of C(sp3)–H bond functionalization and have begun to unlock the potential of these reactions to achieve the site-divergent functionalization of C(sp3)–H bonds, wherein the site of functionalization is changed by modulating the stereoelectronic properties of the catalyst or reagent. This short review will provide a summary of selected examples of catalyst- and reagent-controlled site-divergent intermolecular functionalization of C(sp3)–H bonds, the factors responsible for modulating the site selectivity of these reactions, and will identify potential areas worthy of future research in this field.

Keywords: Catalysis; C–H bond functionalization; C–H bond reactivity; chemoselectivity; Diamond Jubilee Issue; organic chemistry; oxidation; site-divergent reactions; site-selectivity
Corresponding author: Alexander Fawcett, Department of Chemistry, University of California, Berkeley, CA94720, USA, e-mail:
Article note: A collection of peer-reviewed articles by past winners of the IUPAC and IUPAC-SOLVAY International Award for Young Chemists to celebrate the 60th anniversary of Pure and Applied Chemistry.

About the author

Alexander Fawcett

Alexander Fawcett completed his MSci in Chemistry at the University of Birmingham, UK, in 2014. He then moved to the University of Bristol, UK, where he completed his Ph.D. under the supervision of Professor Varinder K. Aggarwal in 2018. Here, he developed new methods for the preparation of organoboron compounds and investigated the reactivity of novel strained boronate complexes. For this work, he was awarded the 2019 IUPAC-Solvay International Award for Young Chemists and was a finalist for the Reaxys Ph.D. Prize 2019. In late 2018, he moved to the University of California, Berkeley, where he is currently working as a postdoctoral researcher under the supervision of Professor John F. Hartwig on the mechanistically-driven design and development of highly site selective C(sp3)–H bond functionalization reactions and applying them to the late-stage functionalization of complex molecules.

  1. Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Published Online: 2020-09-28
Published in Print: 2020-12-16

© 2020 IUPAC & De Gruyter. This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. For more information, please visit: http://creativecommons.org/licenses/by-nc-nd/4.0/

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Preface
  4. Pure and Applied Chemistry Diamond Jubilee Issue
  5. Invited papers
  6. Harnessing host–guest interactions to control structure at the nanoscale
  7. Corrole photochemistry
  8. Restructuring of ultra-thin branches in multi-nucleated silicon nanowires
  9. Multidimensional graphene nanostructures – synthesis and applications
  10. Electrochemical flow systems enable renewable energy industrial chain of CO2 reduction
  11. A retrospective on MXene-based composites for solar fuel production
  12. Radicals in prebiotic chemistry
  13. Advances in the catalyst- and reagent-controlled site-divergent intermolecular functionalization of C(sp3)–H bonds
  14. Reaction of Amines with NO at room temperature and atmospheric pressure: is nitroxyl a reaction intermediate?
  15. A Puerto Rican chemist with coffee
https://doi.org/10.1515/pac-2020-0803
Keywords for this article
Catalysis; C–H bond functionalization; C–H bond reactivity; chemoselectivity; Diamond Jubilee Issue; organic chemistry; oxidation; site-divergent reactions; site-selectivity

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Preface
  4. Pure and Applied Chemistry Diamond Jubilee Issue
  5. Invited papers
  6. Harnessing host–guest interactions to control structure at the nanoscale
  7. Corrole photochemistry
  8. Restructuring of ultra-thin branches in multi-nucleated silicon nanowires
  9. Multidimensional graphene nanostructures – synthesis and applications
  10. Electrochemical flow systems enable renewable energy industrial chain of CO2 reduction
  11. A retrospective on MXene-based composites for solar fuel production
  12. Radicals in prebiotic chemistry
  13. Advances in the catalyst- and reagent-controlled site-divergent intermolecular functionalization of C(sp3)–H bonds
  14. Reaction of Amines with NO at room temperature and atmospheric pressure: is nitroxyl a reaction intermediate?
  15. A Puerto Rican chemist with coffee
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