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) |
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).