Table 5. Summary of Tandem Deacetalization–Knoevenagel Reaction Employing Bifunctional MOFsa.
| Sr. No. | MOF compound | Reactive site | Reactants | Products | Reaction conditions | Ref |
|---|---|---|---|---|---|---|
| 1 | Yb-BDC-NH2Dy-BDC-NH2Sm-BDC-NH2 | Yb3+Dy3+Sm3+, -NH2 | BDA and MN | 2-benzylidenemalononitrile | DMSO-d6 (2 mL), catalyst (100 mg), 50 °C, 24 h | (291) |
| 2 | 3.1% Ru/UiO-66 | Ru2+, Zn2+ | BA and MN | 2-benzylidenemalononitrile | toluene (1.5 mL), O2 1 atm,100 °C | (292) |
| 3 | HNUST-8 | Cu2+, acylamide | BDA and MN | 2-benzylidenemalononitrile | DMSO, 50 °C, 48 h, 0.5 mol % HNUST-8 | (293) |
| 4 | HNUST-6 | Cu2+, acylamide | BDA and MN | 2-benzylidenemalononitrile | 0.5 mol % catalyst, DMSO, 50 °C, 48 h | (294) |
| 5 | [Zn5(L)4(OH)2(H2O)4]n·8n(DMF)·4n(H2O) | Zn2+, – NH | BDA and MN | 2-benzylidenemalononitrile | 1 mol % of catalyst 1 or 2, DMF (0.5 mL), 80 °C, 3 h | (295) |
| 6 | Cz-MOF-253-800 | Al3+, N | BD and MN | 2-benzylidenemalononitrile | 2 mL of toluene, and 5 mg of Pd/Cz-MOF-253–800, 80 °C, 17 h, 150 psi H2 | (296) |
| 7 | ZIF-8,UiO-66(Zr)-NH2,MIL-101(Cr)-NH2) | Zn2+, O2–, N–, -OH, -NH2 | BDA and MN | 2-benzylidenemalononitrile | 100 °C, 3 h in the Pickering emulsions consisting of water (3 mL)–toluene (2 mL) MOFs (50 mg) | (297) |
| 8 | CSMCRI-15 | Cd2+, -N=N–NH2 | BDA and MN | 2-benzylidenemalononitrile | 2 mol % catalyst, 4 h, 60 °C, solvent free | (298) |
| 9 | H-ZIF-8/Au@mSiO2 | Au, Zn2+, -N- | p-nitro BD and MN | 2-(4-nitrobenzylidene)malononitrile | catalyst (30 mg) and 2.0 mL tetrahydrofuran at 30 °C for 0.5 h | (299) |
| 10 | Hf-UiO-66-N2H3 | Hf, N2H3 | BD, MN | 2-benzylidenemalononitrile | ethanol (0.3 mL), catalyst (20 mg), RT, 4 h | (300) |
| 11 | NUC-29 | Cd2+, Npyridine | BDA, MN | 2-benzylidenemalononitrile | 1.0 mol %, based on the {Cd} center, DMSO 50 mL, 5 h, 70 °C | (301) |
| 12 | NUC – 53 | Zn2+, Npyridine | BDA, MN | 2-benzylidenemalononitrile | 0.3 mol %, DMSO 3 mL, 6h, 70 °C | (302) |
| 13 | UiO-67-(NH2)2 | Zr4+, -NH2 | BDA, MN | 2-benzylidenemalononitrile | ethanol (0.3 mL) and catalyst (15 mg) 10 h, 60 °C | (303) |
| 14 | IRA900(xOH)-MIL-101(Al)-NH2 | Al3+, -NH2 | BDA, MN | 2-benzylidenemalononitrile | solvent free, catalyst 0.3 g, 5 h at 110 °C | (304) |
| 15 | Cu(ABDC)(DMF) | Cu2+, -NH2 | BDA, MN | 2-benzylidenemalononitrile | d3-acetonitrile, 0.1 mol % catalyst, 24 h, 60 °C | (305) |
| 16 | Zr12BDC-NH2 | Zr4+, -NH2 | BDA, MN | 2-benzylidenemalononitrile | CDCl3 (1.5 mL), catalyst, 55 °C, 24 h, 100 mg | (306) |
| 17 | MIL-101(Cr)@PMF | Cr3+, -NH-NH2 | BDA, MN | 2-benzylidenemalononitrile | 30 mg catalyst, 12 h, 4 mL ethanol, 65 °C | (307) |
| 18 | [(CH3)2NH2]2[BaZn(TDP)(H2O)]·DMF·5H2O, (NUC-51) | Zn2+, Ba2+, -COOH, Npyridine | BDA, MN | 2-benzylidenemalononitrile | 1.0 mol % catalyst, 5 mL (DMSO) 4 h 70 °C | (308) |
| 19 | (Me2NH2)[InZn(TDP)(OH2)]·4DMF·4H2O (NUC-42) | Zn2+, In3+, −COOH, Npyridine | BDA, MN | 2-benzylidenemalononitrile | DMSO, 5 mL. 8h, 60 °C, 1 mol % catalyst | (309) |
| 20 | MIL-101(Cr)@MOF-867 | Cr3+, Zn2+, -C=N | BDA, MN | 2-benzylidenemalononitrile | 20 mg, 70 °C, 12 h, DMSO (4 mL) | (310) |
a
Abbreviations: BA = benzyl alcohol, MN = malononitrile; BDC-NH2 = 2-aminobenzenedicarboxylate; BDA = benzaldehyde dimethyl acetal; PDBAD = 4′,4‴-((pyridine-3,5-dicarbonyl)bis(azanediyl))bis[1,1′-biphenyl]-3,5-dicarboxylic acid; MOPBB = (5-methoxy-isophthaloyl)-bis(azanediyl)]diisophthalic acid; 1,4-BDC = 1,4-benzene dicarboxylate; BD = benzaldehyde; H3TCA = 4,4′,4′-tri- carboxytriphenylamine; DPA = (E)-1,2-di(pyridin-4-yl)diazene; 2-MeIm = 2-methylimidazole; 2- H2BDC-N2H3 = hydrazinyl-1,4-benzenedicarboxylic acid; H6TDP - 2,4,6-tris(2,4-dicarboxyphenyl)pyridine; ABDC = 2,2′-diamino-[1,1′-biphenyl]-4,4′-dicarboxylic acid; PMF = polymelamine formaldehyde.