850568-54-6

Basic information

• Product Name: 4-(TERT-BUTOXYCARBONYL)PHENYLBORONIC ACID
• Synonyms: T-BUTYL 4-BORONOBENZOATE;4-(TERT-BUTOXYCARBONYL)BENZENEBORONIC ACID;4-(TERT-BUTOXYCARBONYL)PHENYLBORONIC ACID;4-(T-BUTOXYCARBONYL)PHENYLBORONIC ACID;tert-Butyl 4-boronobenzoate;Benzoic acid,4-borono-, 1,1-diMethylethyl ester;4-(tert-Butoxycarbonyl)phenylboronic Acid (contains varying amounts of Anhydride)
• CAS NO: 850568-54-6
• Molecular Formula: C₁₁H₁₅BO₄
• Molecular Weight: 222.05
• Product Categories: blocks;BoronicAcids;Carboxes;Benzene series
• Mol File: 850568-54-6.mol
• Article Data: 2

Chemical Properties

• Melting Point: 100-106°C
• Boiling Point: 364.3 ºC at 760 mmHg
• Flash Point: 174.1 ºC
• Appearance: /
• Density: 1.15 g/cm³
• Vapor Pressure: 6.04E-06mmHg at 25°C
• Refractive Index: 1.517
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• PKA: 8.02±0.16(Predicted)
• Water Solubility: Slightly soluble in water.
• CAS DataBase Reference: 4-(TERT-BUTOXYCARBONYL)PHENYLBORONIC ACID(CAS DataBase Reference)
• NIST Chemistry Reference: 4-(TERT-BUTOXYCARBONYL)PHENYLBORONIC ACID(850568-54-6)
• EPA Substance Registry System: 4-(TERT-BUTOXYCARBONYL)PHENYLBORONIC ACID(850568-54-6)

Safety Data

• Statements: 36/37/38
• Safety Statements: 26-36/37/39
• HazardClass: IRRITANT
• Hazardous Substances Data: 850568-54-6(Hazardous Substances Data)

Usage

Uses

Benzene boronic acid mediated the ortho specific hydroxyalkylation of phenols by aldehydes. The ability of boronic acids to reversibly bind diol functional groups has been utilized for fluorescent detection of saccharides. It can be a effective catalyst for amidation and esterification of carboxylic acids.

InChI:InChI=1/C11H15BO4/c1-11(2,3)16-10(13)8-4-6-9(7-5-8)12(14)15/h4-7,14-15H,1-3H3

Synthetic route

4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzoic acid tert-butyl ester → (4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6)

Conditions	Yield
With sodium periodate; ammonium acetate In water; acetone at 20℃; for 12h;	83%

4-carboxyphenylboronic acid (14047-29-1) + isobutene (115-11-7) → (4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6)

Conditions	Yield
With sulfuric acid In dichloromethane at 20℃; for 24h;

4-chlorobenzoyl chloride (586-75-4) → (4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6)

Conditions	Yield
Multi-step reaction with 3 steps 1: diethyl ether / 1 h / 0 °C 2: potassium acetate; palladium bis[bis(diphenylphosphino)ferrocene] dichloride / 1,4-dioxane / 36 h / 100 °C / Inert atmosphere 3: ammonium acetate; sodium periodate / acetone; water / 12 h / 20 °C View Scheme

tert-butyl-4-bromobenzoate (59247-47-1) → (4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium acetate; palladium bis[bis(diphenylphosphino)ferrocene] dichloride / 1,4-dioxane / 36 h / 100 °C / Inert atmosphere 2: ammonium acetate; sodium periodate / acetone; water / 12 h / 20 °C View Scheme

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + p-toluenesulfonic acid 3,5-dibromo(pyridin-2-yl) ester (882029-80-3) → di-tert-butyl 4,4’-[2-(tosyloxy)pyridine-3,5-diyl]dibenzoate

Conditions	Yield
With palladium diacetate; potassium carbonate; di(1-adamantyl)benzylphosphine In toluene at 50℃; for 0.833333h; Suzuki-Miyaura Coupling; Inert atmosphere; chemoselective reaction;	99%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 4,6-dibromo-2-tosyloxypyridine → di-tert-butyl 4,4’-[6-(tosyloxy)pyridine-2,4-diyl] dibenzoate

Conditions	Yield
With palladium diacetate; potassium carbonate; di(1-adamantyl)benzylphosphine In toluene at 50℃; for 0.5h; Suzuki-Miyaura Coupling; Inert atmosphere; chemoselective reaction;	99%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 5-bromo-2-(4-methylphenylsulfonyloxy)pyridine → tert-butyl 4-[6-(tosyloxy)pyridin-3-yl]benzoate

Conditions	Yield
With palladium diacetate; C27H37P*H3P; potassium carbonate In water; toluene at 25℃; for 1.5h; Suzuki-Miyaura Coupling; Sealed tube; Inert atmosphere; chemoselective reaction;	99%
With palladium diacetate; potassium carbonate; di(1-adamantyl)benzylphosphine In water; toluene Suzuki-Miyaura Coupling; Inert atmosphere; regioselective reaction;	99%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 4-bromopyridin-2-yl 4-methylbenzenesulfonate → tert-butyl 4-(2-(tosyloxy)pyridin-4-yl)benzoate

Conditions	Yield
With palladium diacetate; C27H37P*H3P; potassium carbonate In water; toluene at 25℃; for 3.5h; Suzuki-Miyaura Coupling; Sealed tube; Inert atmosphere; chemoselective reaction;	97%
With palladium diacetate; potassium carbonate In water; toluene for 3.5h; Suzuki-Miyaura Coupling; Inert atmosphere; regioselective reaction;	97%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + methyl 2-amino-4-chloro-5-iodobenzoate (199850-56-1) → C19H20ClNO4

Conditions	Yield
With dichloro[1,1'-bis(di-t-butylphosphino)ferrocene]palladium(II); potassium carbonate In water; acetonitrile for 48h; Suzuki Coupling; Inert atmosphere; Reflux;	96%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 1-acetyl-5-phenyl-4,5-dihydro-1H-pyrazol-3-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (1180009-36-2) → tert-butyl 4-(1-acetyl-5-phenyl-4,5-dihydro-1H-pyrazol-3-yl)benzoate (1180009-48-6)

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate In ethanol; water; toluene at 120℃; for 0.166667h; Suzuki cross-coupling; Inert atmosphere; Microwave irradiation;	95%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 2-amino-5-bromo-3-phenylmethylpyrazine (174680-55-8) → tert-butyl 4-(5-amino-6-benzylpyrazin-2-yl)benzoate

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; caesium carbonate In 1,4-dioxane at 75℃; for 0.5h;	92%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 1-bromo-4-methoxy-benzene (104-92-7) → 4-tert-butoxycarbonyl-4'-methoxy-1,1'-biphenyl (944385-73-3)

Conditions	Yield
With palladium diacetate In ethanol at 20℃; for 0.25h; Suzuki-Miyaura Coupling;	92%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + (2-hydroxyethyl)(methyl)amine (109-83-1) + Glyoxal (131543-46-9) → tert-butyl 4-(2-hydroxy-4-methylmorpholin-3-yl)benzoate

Conditions	Yield
Stage #1: (4-(tert-butoxycarbonyl)phenyl)boronic acid; (2-hydroxyethyl)(methyl)amine In ethanol; water at 60℃; for 0.25h; Petasis Reaction; Inert atmosphere; Stage #2: Glyoxal In ethanol; water at 60℃; for 24h; Petasis Reaction; Inert atmosphere;	92%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 5-phenylpyridin-2-yl 4-methylbenzenesulfonate → tert-butyl 4-(5-phenylpyridin-2-yl)benzoate

Conditions	Yield
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; potassium carbonate In water; toluene at 100℃; for 1h; Suzuki-Miyaura Coupling; Sealed tube; Inert atmosphere; Schlenk technique;	92%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 3-bromopyridin-2-yl trifluoromethanesulfonate → tert-butyl 4-[2-[[(trifluoromethyl)sulfonyl]oxy]pyridin-3-yl]-benzoate

Conditions	Yield
With palladium diacetate; C27H37P*H3P; potassium carbonate In water; toluene at 25℃; for 4h; Suzuki-Miyaura Coupling; Sealed tube; Inert atmosphere; chemoselective reaction;	90%
With palladium diacetate; potassium carbonate In water; toluene for 2h; Suzuki-Miyaura Coupling; Inert atmosphere; regioselective reaction;	90%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 5-bromo-2-pyridylamine (1072-97-5) → tert-butyl 4-(6-aminopyridin-3-yl)benzoate

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate In 1,4-dioxane; water at 80℃; for 2h; Suzuki-Miyaura Coupling; Inert atmosphere;	89%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 6-((2-chloro-6-fluorophenoxy)methyl)-3-iodo-1-((3-(trifluoromethyl)phenyl)sulfonyl)-1H-indole → tert-butyl 4-(6-((2-chloro-6-fluorophenoxy)methyl)-1-((3-(trifluoromethyl)phenyl)sulfonyl)-1H-indol-3-yl)benzoate

Conditions	Yield
With triphenylphosphine; cesium fluoride; bis(dibenzylideneacetone)-palladium(0) In 1,2-dimethoxyethane at 90℃; Inert atmosphere; Sealed tube;	89%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 12-chloro-6-phenyl-5,6,7,12-tetrahydrodibenzo[c,f ][1,5]azastibocine (1609694-04-3) → tert-butyl 4-(6-phenyl-6,7-dihydrodibenzo[c,f][1,5]azastibocin-12(5H)-yl)benzoate

Conditions	Yield
With water; nickel diacetate; sodium carbonate In toluene at 100℃; for 20h; Inert atmosphere; Schlenk technique;	89%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 5-bromo-2-aminopyrimidine (7752-82-1) → tert-butyl 4-(2-aminopyrimidin-5-yl)benzoate (1029715-16-9)

Conditions	Yield
With sodium carbonate; tetrakis(triphenylphosphine) palladium(0) In ethanol; water; toluene at 120℃; for 3h;	86.6%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + (R)-3-bromo-6-((4-hydroxy-1-(3-phenylbutanoyl)piperidin-4-yl)methyl)-2-methyl-2,6-dihydro-7H-pyrazolo[4,3-d]pyrimidin-7-one → tert-butyl (R)-4-(6-((4-hydroxy-1-(3-phenylbutanoyl)piperidin-4-yl)methyl)-2-methyl-7-oxo-6,7-dihydro-2H-pyrazolo[4,3-d]pyrimidin-3-yl)benzoate

Conditions	Yield
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane; water at 120℃; for 0.5h; Suzuki Coupling; Inert atmosphere; Microwave irradiation; Sealed tube;	85%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + p-nitrobenzene iodide (636-98-6) → 4-(4-nitrophenyl)-benzoic acid tert-butyl ester (914659-71-5)

Conditions	Yield
With sodium carbonate; tetrakis(triphenylphosphine) palladium(0) In ethanol; water; toluene for 12h; Suzuki coupling; Heating;	84%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate (1350915-26-2) → tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate (1392113-09-5)

Conditions	Yield
With sodium carbonate monohydrate; tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane; water; isopropyl alcohol for 3.5h; Suzuki Coupling; Inert atmosphere;	83%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 5-amino-4-methyl-1-phenyl-1H-pyrazol-3-yl trifluoromethane sulfonate (1414578-42-9) → C21H23N3O2

Conditions	Yield
With potassium phosphate; chloro(2-dicyclohexylphosphino-2’,4’,6’-triisopropyl-1,1‘-biphenyl)[2-(2’-amino-1,1‘-biphenyl’)]palladium(II) In 1,4-dioxane at 90℃; for 6h;	83%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 5-bromo-tetrandrine (62067-29-2) → 5-(4-t-butyloxycarbonylphenyl)tetrandrine

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium carbonate In water; toluene for 24h; Suzuki-Miyaura Coupling; Reflux;	81%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + Glyoxal (131543-46-9) + toluene-4-sulfonic acid (104-15-4) + N-Benzylethanolamine (104-63-2) → tert-butyl 4-(4-benzyl-2-hydroxymorpholin-3-yl)benzoate 4-toluenesulfonate

Conditions	Yield
Stage #1: (4-(tert-butoxycarbonyl)phenyl)boronic acid; N-Benzylethanolamine at 115℃; for 0.333333h; Petasis Reaction; Inert atmosphere; Stage #2: Glyoxal In water at 115℃; for 1h; Petasis Reaction; Inert atmosphere; Stage #3: toluene-4-sulfonic acid In ethyl acetate at 50℃; Inert atmosphere;	81%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 3-bromo-4H-thiochromen-4-one (68847-94-9) → tert-butyl 4-(4-oxo-4H-thiochromen-3-yl)benzoate (1338224-17-1)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 60℃; for 72h; Suzuki-Miyaura coupling; Inert atmosphere;	80%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + (((azidosulfonyl)(methyl)amino)methyl)benzene → C19H24N2O4S

Conditions	Yield
With copper(l) chloride In methanol at 20℃; for 3h; Chan-Lam Coupling;	80%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 5-bromo-2-methoxybenzaldehyde (25016-01-7) → 3'-formyl-4'-methoxybiphenyl-4-carboxylic acid tert-butyl ester

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In 1,4-dioxane; water for 4h; Suzuki Coupling; Inert atmosphere; Sealed tube; Heating;	79%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 1,1-dimethylethyl 3-bromo-5-{6-[(N-{[(1,1-dimethylethyl)oxy]carbonyl}-β-alanyl)amino]-3-pyridinyl}-1H-pyrrolo[2,3-b]pyridine-1-carboxylate (890842-91-8) → 1,1-dimethylethyl 3-bromo-5-{6-[(N-{[(1,1-dimethylethyl)oxy]carbonyl}-β-alanyl)amino]-3-pyridinyl}-3-(4-{[(1,1-dimethylethyl)oxy]carbonyl}phenyl)-1H-pyrrolo[2,3-b]pyridine-1-carboxylate (890842-92-9)

Conditions	Yield
With potassium carbonate; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In 1,4-dioxane; water at 80℃; for 1.5h; Suzuki Coupling;	78%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + 2-bromo-5-[4-(3,4-dichloro-phenyl)-thiazol-2-yl]-benzoic acid methyl ester (1428482-15-8) → 4-[4-(3,4-dichloro-phenyl)-thiazol-2-yl]-biphenyl-2,4'-dicarboxylic acid 4'-tert-butyl ester 2-methyl ester (1428482-16-9)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 95 - 100℃; Inert atmosphere;	78%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + Fmoc-4-bromo-L-phenylalanine → (2S)-3-(4-{4-[(tert-butoxy)carbonyl]phenyl}phenyl)-2-({[(9H-fluoren-9-yl)methoxy]carbonyl}amino)propanoic acid

Conditions	Yield
With potassium phosphate; 1,1'-bis(di-tertbutylphosphino)ferrocene; palladium diacetate In tetrahydrofuran at 50℃; for 16h; Suzuki-Miyaura Coupling; Inert atmosphere;	78%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + benzyl N-[2-(4-bromophenyl)ethyl]carbamate (191170-76-0) → C27H29NO4 (1146546-95-3)

Conditions	Yield
With sodium carbonate; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In water; N,N-dimethyl-formamide at 85℃; for 18.1667h;	77%

(4-(tert-butoxycarbonyl)phenyl)boronic acid (850568-54-6) + sodium carbonate monohydrate + (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-benzyl 5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(((trifluoromethyl)sulfonyl)oxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (1350915-20-6) + isopropyl alcohol (67-63-0) → (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(tert-butoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (1621533-75-2)

Conditions	Yield
With tetrakis(triphenylphosphine)palladium (0) In 1,4-dioxane; water	77%

Upstream product

• 14047-29-1 4-carboxyphenylboronic acid 
• 115-11-7 isobutene 
• 586-75-4 4-chlorobenzoyl chloride 
• 59247-47-1 tert-butyl-4-bromobenzoate 
• 850568-72-8 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzoic acid tert-butyl ester 

Downstream Products

• 890842-85-0 tert-butyl 5-{6-[(tert-butoxycarbonyl)amino]pyridin-3-yl}-3-[4-(tert-butoxycarbonyl)phenyl]-1H-pyrrolo[2,3-b]pyridine-1-carboxylate 
• 890842-92-9 1,1-dimethylethyl 3-bromo-5-{6-[(N-{[(1,1-dimethylethyl)oxy]carbonyl}-β-alanyl)amino]-3-pyridinyl}-3-(4-{[(1,1-dimethylethyl)oxy]carbonyl}phenyl)-1H-pyrrolo[2,3-b]pyridine-1-carboxylate 
• 1029715-16-9 tert-butyl 4-(2-aminopyrimidin-5-yl)benzoate 
• 1073129-53-9 methyl 7-(4-tert-butoxycarbonylphenyl)-4-hydroxy-1-methyl-2-oxo-1,2-dihydroquinoline-3-carboxylate 
• 1101173-96-9 tert-butyl 4-(3-bromo-1,2,4-thiadiazol-5-yl)phenylcarbamate 
• 955406-66-3 (R)-3-(3,5-dichloro-4'-t-butoxycarbonyl-biphenyl-4-ylmethyl)-1-(1-trifluoromethanesulfonyl-4,5,6,7-tetrahydro-1H-indazol-4-yl)-pyrrolidin-2-one 
• 955406-67-4 (R)-3-(3,5-dichloro-4'-t-butoxycarbonyl-biphenyl-4-ylmethyl)-1-(2-trifluoromethanesulfonyl-4,5,6,7-tetrahydro-2H-indazol-4-yl)-pyrrolidin-2-one 
• 1146546-95-3 C₂₇H₂₉NO₄ 
• 1185856-30-7 tert-butyl 4-(2-amino-5-methylpyrimidin-4-yl)benzoate 
• 1180009-48-6 tert-butyl 4-(1-acetyl-5-phenyl-4,5-dihydro-1H-pyrazol-3-yl)benzoate 
• 1195951-40-6 C₂₇H₂₁Cl₂F₃N₂O₄ 
• 1195951-58-6 C₂₀H₁₇BrCl₂N₂O₃ 
• 1195951-71-3 C₃₀H₂₆F₆N₂O₅ 
• 1258878-92-0 tert-butyl 4-(5-bromopyridin-2-yl)benzoate 

Relevant articles and documents

A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal-Organic Framework

We describe a new strategy to generate non-coordinating anions using zwitterionic metal-organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO2)4]-) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of MnIII- and FeIII-porphyrins in the zwitterionic MOFs in three representative electrocyclization reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition of aziridines and alkenes, and [4 + 2] hetero-Diels-Alder cycloaddition of aldehydes with dienes. This work paves a new way to design functional MOFs for tunable chemical catalysis.