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Radical Reactions Enabled By Porphyrinoids

Wednesday, 1 June 2022: 14:40
West Meeting Room 205 (Vancouver Convention Center)
D. Gryko (Institute of Organic Chemistry PAS)
Look deep into nature, and then you will understand everything better.”

Albert Einstein

Porphyrinoids, also known as the pigments of life, are a class of naturally occurring organic dyes. They play key roles in crucial processes that support life - oxygen transport (hem), electron transport (cytochrome c), photosynthesis (chlorophyll a), and synthesis of DNA (vitamin B12). Vitamin B12 - a co-factor in many catalytic processes. Following nature, we have been exploiting the potential of this compound in catalysis.

Vitamin B12 - catalysis has been successfully translated into the laboratory and used in a small collection of reactions.[1-2] The advantage of using vitamin B12 as a catalyst lays in the complete stability of the central cobalt ion and by the definition it is nontoxic. It has also been well documented that the reaction mechanism usually follows a radical pathway, bringing a new dimension to this already interesting field.[2]

Along this line, we have developed new vitamin B12-catalyzed reactions involving reduction of Co(III) to Co(I) or Co(II) and subsequent reactions with electrophiles or radicals. Vitamin B12 derivative unusually catalyzes a new olefinic sp2 C-H alkylation reaction with diazo reagents as a carbene source,[3], acylation of activated olefins, alkylation of strained molecules.[4-6] These key findings emphasize the unique feature of vitamin B12 as a catalyst to achieve something unachievable with other methodologies or to find a greener approach.

References

  • [1] Banerjee, R. Chemistry and Biochemistry of B12, John Wiley & Sons, Inc, 1999
  • [2] Giedyk, M., Goliszewska, K., Gryko, D. Soc. Rev. 2015, 44, 3391-3404.
  • [3] Giedyk, M.; Fedosov, S.; Gryko, D. Commun. 2014, 50, 4674-4676.
  • [4] Ociepa, A. J. Wierzba, J. Turkowska, D. Gryko, J. Am. Chem. Soc. 2020, 142, 5355-5361.
  • [5] Potrząsaj, A.; Musiejuk, M.; Chaładaj, W.; Giedyk, M; Gryko, D ChemRxiv, 2021, 143, 9368–9376. https://doi.org/10.26434/chemrxiv.13559852.v1
  • [6] Turkowska, J.; Durka, J.; Ociepa, M.; Gryko, D. Chem. Commun., 2021, DOI https://doi.org/10.1039/D1CC05330B