Sustainable manganese catalysis for late-stage C–H functionalization of bioactive structural motifs

Jongwoo Son

Review
Published 26 Jul 2021

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1. Graphical Abstract
2. Scheme 1: Mn-catalyzed late-stage fluorination of sclareolide (1) and complex steroid 3.
  
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3. Figure 1: Proposed reaction mechanism of C–H fluorination by a manganese porphyrin catalyst.
  
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4. Scheme 2: Late-stage radiofluorination of biologically active complex molecules.
  
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5. Figure 2: Proposed mechanism of C–H radiofluorination.
  
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6. Scheme 3: Late-stage C–H azidation of bioactive molecules. ^a1.5 mol % of Mn(TMP)Cl (5) was used. ^bMethyl acet...
  
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7. Figure 3: Proposed reaction mechanism of manganese-catalyzed C–H azidation.
  
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8. Scheme 4: Mn-catalyzed late-stage C–H azidation of bioactive molecules via electrophotocatalysis. ^a2.5 mol % ...
  
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9. Figure 4: Proposed reaction mechanism of electrophotocatalytic azidation.
  
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10. Scheme 5: Manganaelectro-catalyzed late-stage azidation of bioactive molecules.
  
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11. Figure 5: Proposed reaction pathway of manganaelectro-catalyzed late-stage C–H azidation.
  
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12. Scheme 6: Mn-catalyzed late-stage amination of bioactive molecules. ^a3 Å MS were used. Protonation with HBF₄⋅...
  
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13. Figure 6: Proposed mechanism of manganese-catalyzed C–H amination.
  
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14. Scheme 7: Mn-catalyzed C–H methylation of heterocyclic scaffolds commonly found in small-molecule drugs. ^aDAS...
  
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15. Scheme 8: Examples of late-stage C–H methylation of bioactive molecules. ^aDAST activation. ^bFor insoluble sub...
  
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16. Scheme 9: A) Mn-catalyzed late-stage C–H alkynylation of peptides. B) Intramolecular late-stage alkynylative ...
  
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17. Figure 7: Proposed reaction mechanism of Mn(I)-catalyzed C–H alkynylation.
  
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18. Scheme 10: Late-stage Mn-catalyzed C–H allylation of peptides and bioactive motifs.
  
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19. Scheme 11: Intramolecular C–H allylative cyclic peptide formation.
  
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20. Scheme 12: Late-stage C–H glycosylation of tryptophan analogues.
  
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21. Scheme 13: Late-stage C–H glycosylation of tryptophan-containing peptides.
  
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22. Scheme 14: Late-stage C–H alkenylation of tryptophan-containing peptides.
  
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23. Scheme 15: A) Late-stage C–H macrocyclization of tryptophan-containing peptides and B) traceless removal of py...
  
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