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1
Aldehyde oxidation is one of the key processes in the Biological systems.
ALDHs is one of the enzyme which catalyses the detoxification of the
aldehydes in our body by converting it into acid.
Most aldehydes are generally inert to
autoxidation and requires strong oxidant.
2
3
J. Am. Chem. Soc. 2018, 140, 16037−16041
• They have reported the electrophilic oxidation of aldehydes by metal oxygen
intermediate which is very rare to found.
• Analysed the reactivity by kinetic studies.
• DFT calculations was also done to verify the different steps in the reaction
mechanism and founded rds.
• Catalytic oxidation and comparison of various aldehydes was done and
evaluated.
4
5
From van’t Hoff plot
ΔH° = −9.4 kcal mol−1
ΔS° = −31.9 cal mol−1 K−1
ΔG° = −0.1 kcal mol−1
From Eyring Plot
ΔH⧧ = 18.2 kcal mol−1
ΔS⧧ = −1.6 cal mol−1 K−1
ΔG⧧ = 18.7 kcal mol−1
6
Metalation of L(i)
Determination of electronic nature using Benzaldehyde
Negative value of σp
+ and rate of aldehydes, 3°-
CHO > 2°-CHO > 1°-CHO, indicates the
electrophillic nature of the 1.
7
The KIE value is obtained as 2.0, indicating
that the rate-determining step includes the
C−H bond activation of benzaldehyde.
8
9
10
References
11

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CYS7040.pptx

  • 1. 1
  • 2. Aldehyde oxidation is one of the key processes in the Biological systems. ALDHs is one of the enzyme which catalyses the detoxification of the aldehydes in our body by converting it into acid. Most aldehydes are generally inert to autoxidation and requires strong oxidant. 2
  • 3. 3 J. Am. Chem. Soc. 2018, 140, 16037−16041
  • 4. • They have reported the electrophilic oxidation of aldehydes by metal oxygen intermediate which is very rare to found. • Analysed the reactivity by kinetic studies. • DFT calculations was also done to verify the different steps in the reaction mechanism and founded rds. • Catalytic oxidation and comparison of various aldehydes was done and evaluated. 4
  • 5. 5
  • 6. From van’t Hoff plot ΔH° = −9.4 kcal mol−1 ΔS° = −31.9 cal mol−1 K−1 ΔG° = −0.1 kcal mol−1 From Eyring Plot ΔH⧧ = 18.2 kcal mol−1 ΔS⧧ = −1.6 cal mol−1 K−1 ΔG⧧ = 18.7 kcal mol−1 6
  • 7. Metalation of L(i) Determination of electronic nature using Benzaldehyde Negative value of σp + and rate of aldehydes, 3°- CHO > 2°-CHO > 1°-CHO, indicates the electrophillic nature of the 1. 7
  • 8. The KIE value is obtained as 2.0, indicating that the rate-determining step includes the C−H bond activation of benzaldehyde. 8
  • 9. 9
  • 10. 10