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. 2023 Nov 11;4(1):59–90. doi: 10.1021/acsorginorgau.3c00033

Table 6. Summary of Other Cascade Reactions Employing Bifunctional MOFsa.

Reaction name Sr. No. MOF compound Reactive site Reactants Product Conditions Ref
Multicomponent Hanstch Reaction 1 OMS-MIL-101(Cr) Cr, NH2, aromatic aldehydes, dimedone, β-ketoesters ammonium acetate methyl 2,7,7-trimethyl-5-oxo-4-phenyl-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate 4 mol % of cat., EtOH (146)
2 MIL-101(Cr)-N(CH2PO3H2)2 Cr -NH2, -PO3, -OH, O ethyl cyanoacetate or ethyl acetoacetate, hydrazine hydrate, malononitrile, aldehydes N-amino-2-pyridone and pyrano [2,3-c]pyrazole 5–10 mol % cat. (139)
Chromene Synthesis 3 Zn-Bp-BTC MOF N, O, -OH benzaldehyde, malononitrile, and active methylene dimedone 2-amino-4H-chromene 0.06 mmol cat., ethanol (147)
4 zinc(II)-L1/L2/L3/L4 Zn, -NH2 aldehyde malononitrile 1,3-diketone chromene EtOH (2 mL), RT, 2 h, air (149)
Henry Condensation–Fridel Craft Alkylation 5 (Zr)MOF-808 Zr, lysine benzaldehyde, nitromethane, indole 1-(2-nitro-1-phenylethyl)-1H-indene 25 mg cat., 30 °C (148)
Oxidation–Knoevenagel Cascade Reaction 6 M2(BTC)(OH)(4-TPT)2(H2O)·(DMA)0.5(H2O) Co, Ni, N benzyl alcohol malononitrile benzylidene 0.25 mmol % cat., air, 400 μL CH3CN, n-dodecane, 12 h, 353 K (150)
  Ni3(BTC)2(4-TPT)2(H2O)6·1.5H2O          
7 Cu3TATAT Cu, N benzyl alcohol malononitrile benzylidene 8 mol % cat., TEMPO (0.5 equiv), 5 mL CH3CN, 75 °C, 1 atm O2, 12 h (151)
8 H5PMo10V2O40@ MIL-101 Mo, V, Cr benzyl alcohol malononitrile benzylidene 0.5 mol % cat., toluene (1 mL) O2, sealed, 120 °C, 24 h (153)
Oxidation–imine Formation 9 SulP1MOF-808(Hf)-Ir/Rh Rh/IrPO3, Hf ketone, benzyl amine N-(cyclopentylmethyl)aniline 1.5 mol % catalyst in 5 mL toluene under 50 bar of H2 at 90 °C for 24 h (145)
10 Zr/Hf-MOF-808 Zr/Hf, defect -OH aniline, benzyl alcohols N,1-diphenylmethanimine T = 120 °C, 0.6 mmol of catalyst and o-xylene as solvent, 2 h (152)
Knoevenagel Condensation–hydrogenation 11 IY-SO3H/Rh@S-ZIF-8 -SO3H, Zn, N p-nitrobenzaldehyde, malononitrile 2-(4-aminobenzylidene) malononitrile toluene (5 mL), 30 °C, 2 h; 2 MPa H2, 80 °C, 12 h (221)
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PDEAEMA = poly[(2-diethylamino)ethyl methacrylate; IY = Integrated yolk; H6TATAT = 5,5′,5″-(1,3,5-triazine-2,4,6-triyl)tris(azanediyl)triisophthalate; AP = 2-aminopyridine; BTC = 1,3,5-benzene tricarboxylate; Bp = 4,4′-bipyridine; N-ferrocenylmethyl-N-butyl dithiocarbamate (L1); N-ferrocenylmethyl-N-ethylmorpholine dithiocarbamate (L2); N-ferrocenylmethyl-N-2-(diethylamino)ethylamine dithiocarbamate (L3); N-4-methoxybenzyl-N-3-methylpyridyl dithiocarbamate (L4).