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. 2021 Sep 29;11(1):19370.
doi: 10.1038/s41598-021-97801-7.

Anodic electrosynthesis of MIL-53(Al)-N(CH2PO3H2)2 as a mesoporous catalyst for synthesis of novel (N-methyl-pyrrol)-pyrazolo[3,4-b]pyridines via a cooperative vinylogous anomeric based oxidation

Sima Kalhor  1 , Mahmoud Zarei  2 , Mohammad Ali Zolfigol  3 , Hassan Sepehrmansourie  1 , Davood Nematollahi  4 , Saber Alizadeh  5 , Hu Shi  6 , Jalal Arjomandi  7
Affiliations

Anodic electrosynthesis of MIL-53(Al)-N(CH2PO3H2)2 as a mesoporous catalyst for synthesis of novel (N-methyl-pyrrol)-pyrazolo[3,4-b]pyridines via a cooperative vinylogous anomeric based oxidation

Sima Kalhor et al. Sci Rep. .

Abstract

In this paper, the MIL-53(Al)-NH2 metal-organic frameworks (MOFs) was prepared based on the anodic electrosynthesis under green conditions. The anodic electrosynthesis as an environmentally friendly procedure was performed in the aqueous solution, room temperature, atmospheric pressure, and in the short reaction time (30 min). Also, the employed procedure was accomplished without the need for the ex-situ salt and base/probase additives as cation source and ligand activating agent at the constant current mode (10.0 mA cm-2). The electrosynthesized MOFs was functionalized with phosphorus acid tags as a novel mesoporous catalyst. This mesoporous catalyst was successfully employed for synthesis of new series (N-methyl-pyrrol)-pyrazolo[3,4-b]pyridines by one-pot condensation reaction of 3-methyl-1-phenyl-1H-pyrazol-5-amine, 3-(1-methyl-1H-pyrrol-2-yl)-3-oxopropanenitrile and various aromatic aldehydes (mono, bis and tripodal). This catalyst proceeded the organic synthetic reaction via a cooperative vinylogous anomeric based oxidation mechanism with a marginal decreasing its catalytic activity after recycling and reusability.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Figure 1
Figure 1
Structure of N-heterocycle rings as drug candidates.
Figure 2
Figure 2
Geminal anomeric effect versus vinylogous anomeric effect.
Figure 3
Figure 3
Synthesis of new (N-methyl-pyrrol)-pyrazolo[3,4-b]pyridines using MIL-53(Al)-N(CH2PO3H2)2.
Figure 4
Figure 4
Preparation of MIL-53(Al)-N(CH2PO3H2)2.
Figure 5
Figure 5
Preparation of 3-(1-methyl-1H-pyrrol-2-yl)-3-oxopropanenitrile.
Figure 6
Figure 6
Preparation of MIL-53(Al)-NH2 using anodic electrosynthesis method.
Figure 7
Figure 7
FT-IR analysis of 2-amino terephthalic acid, phosphorous acid, MIL-53(Al)-NH2 and MIL-53(Al)-N(CH2PO3H2)2.
Figure 8
Figure 8
XRD pattern of MIL-53(Al)-NH2 and MIL-53(Al)-N(CH2PO3H2)2.
Figure 9
Figure 9
EDX analysis and elemental mapping of electro-synthesized MIL-53(Al)-NH2 and MIL-53(Al)-N(CH2PO3H2)2.
Figure 10
Figure 10
Elemental maps (EDX) of C (red); N (yellow); Al (orange); P (blue) and O (green) atoms for MIL-53(Al)-N(CH2PO3H2.
Figure 11
Figure 11
FE-SEM images of MIL-53(Al)-NH2 (a,b) and MIL-53(Al)-N(CH2PO3H2)2(c,d).
Figure 12
Figure 12
N2 adsorption/desorption isotherm and BJH of MIL-53(Al)-N(CH2PO3H2)2 and MIL-53(Al)-N(CH2PO3H2)2.
Figure 13
Figure 13
Thermogravimetric (TGA) analysis of MIL-53(Al)-N(CH2PO3H2)2.
Figure 14
Figure 14
Plausible mechanisms for the synthesis (N-methyl-pyrrol)-pyrazolo[3,4-b]pyridines using MIL-53(Al)-N(CH2PO3H2)2.
Figure 15
Figure 15
Reusability of MIL-53(Al)-N(CH2PO3H2)2.
See this image and copyright information in PMC

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