4294-57-9

Basic information

• Product Name: P-TOLYLMAGNESIUM BROMIDE
• Synonyms: 4-METHYLPHENYLMAGNESIUM BROMIDE;P-TOLYLMAGNESIUM BROMIDE;bromo(4-methylphenyl)-magnesiu;p-tolylmagnesiumbromidesol.;P-TOLYLMAGNESIUM BROMIDE, 0.5M SOLUTION IN DIETHYL ETHER;P-TOLYLMAGNESIUM BROMIDE, 1M SOLUTION IN TETRAHYDROFURAN;p-Tolylmagnesium bromide Solution, ~0.5 M in Diethyl ether;19%intetrahydrofuranca.1mol/L
• CAS NO: 4294-57-9
• Molecular Formula: Br*C₇H₇*Mg
• Molecular Weight: 195.34
• Product Categories: Classes of Metal Compounds;Grignard Reagents;Grignard Reagents & Alkyl Metals;Mg (Magnesium) Compounds;Synthetic Organic Chemistry;Typical Metal Compounds
• Mol File: 4294-57-9.mol
• Article Data: 23

Chemical Properties

• Melting Point: >300℃ (acetonitrile ethyl ether )
• Boiling Point: 65-67 °C
• Flash Point: −1 °F
• Appearance: Clear yellow solution
• Density: 1.002 g/mL at 25 °C
• Storage Temp.: 2-8°C
• BRN: 636491
• CAS DataBase Reference: P-TOLYLMAGNESIUM BROMIDE(CAS DataBase Reference)
• NIST Chemistry Reference: P-TOLYLMAGNESIUM BROMIDE(4294-57-9)
• EPA Substance Registry System: P-TOLYLMAGNESIUM BROMIDE(4294-57-9)

Safety Data

• Hazard Codes: F+,C,F
• Statements: 12-14-19-22-34-66-67-20/21/22-11-37-40
• Safety Statements: 16-26-33-36/37/39-43-45-27
• RIDADR: UN 2924 3/PG 1
• WGK Germany: 1
• F: 10
• HazardClass: 3/8
• PackingGroup: II
• Hazardous Substances Data: 4294-57-9(Hazardous Substances Data)

Usage

Chemical Properties

Clear yellow solution

Uses

p-Tolylmagnesium bromide is a common Grignard reagent. It can also be used in a variety of cross-coupling reactions.

InChI:InChI=1/C7H7.BrH.Mg/c1-7-5-3-2-4-6-7;;/h3-6H,1H3;1H;/q;;+1/p-1/rC7H7BrMg/c1-6-2-4-7(9-8)5-3-6/h2-5H,1H3

Synthetic route

diethyl ether (60-29-7) + bis(p-tolyl)mercury (537-64-4) + phenylmagnesium bromide → para-methylphenylmagnesium bromide (4294-57-9)

para-bromotoluene (106-38-7) → para-methylphenylmagnesium bromide (4294-57-9)

Conditions	Yield
With magnesium In diethyl ether
With iodine; magnesium In tetrahydrofuran for 2h; Irradiation;
With magnesium In tetrahydrofuran

para-bromotoluene (106-38-7) + magnesium (7439-95-4) → para-methylphenylmagnesium bromide (4294-57-9)

Conditions	Yield
With ethylene dibromide In tetrahydrofuran for 3h; Heating / reflux;
In tetrahydrofuran
In tetrahydrofuran Inert atmosphere;
With iodine In tetrahydrofuran at 20℃;

para-bromotoluene (106-38-7) + bis(chloromethyl)phosphinic chloride (13482-64-9) → para-methylphenylmagnesium bromide (4294-57-9)

Conditions	Yield
With sodium iodide; sodium hydrogensulfite; magnesium In tetrahydrofuran; diethyl ether; water; butanone

5-(2-chlorophenyl)-2-(4-methoxybenzyl)tetrazole (179088-99-4) + para-bromotoluene (106-38-7) + nickel(II) acetylacetonate (3264-82-2) → para-methylphenylmagnesium bromide (4294-57-9)

Conditions	Yield
With hydrogenchloride; diisobutylaluminium hydride; magnesium; triphenylphosphine In tetrahydrofuran; toluene

para-methylphenylmagnesium bromide (4294-57-9) → (4,4'-dimethyl-1,1'-biphenyl) (613-33-2)

Conditions	Yield
With iron(III) chloride; 1,2-dichloro-ethane In diethyl ether for 1h; Heating;	100%
With cobalt(II) chloride hexahydrate; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride In tetrahydrofuran at 0℃; for 1h; Inert atmosphere;	99%
With iron(III) chloride; 1,2-dichloro-ethane In tetrahydrofuran at 0℃; for 0.0833333h; Ionic liquid; Inert atmosphere;	99%

((Z)-3-Dimethylamino-2-phenyl-allylidene)-dimethyl-ammonium; perchlorate (7089-34-1) + para-methylphenylmagnesium bromide (4294-57-9) → (E)-2-phenyl-3-(p-tolyl)acrylaldehyde (79542-20-4)

Conditions	Yield
In tetrahydrofuran 1.) reflux, 3 h, 2.) room temperature, overnight;	100%

para-methylphenylmagnesium bromide (4294-57-9) + 1-{2-[(SS)-(p-tolylsulfinyl)]}pyrrolyl cinnamate (188608-74-4) → C27H24(2)HNO2S

Conditions	Yield
Stage #1: para-methylphenylmagnesium bromide With copper(l) iodide In tetrahydrofuran at -30℃; for 0.5h; Stage #2: 1-{2-[(SS)-(p-tolylsulfinyl)]}pyrrolyl cinnamate In tetrahydrofuran at -30℃; for 1h; Stage #3: With water-d2 In tetrahydrofuran at 20℃; for 12h;	100%

N-methoxy-N-methylcyclohexanecarboxamide (80783-98-8) + para-methylphenylmagnesium bromide (4294-57-9) → cyclohexyl(p-tolyl)methanone (2789-44-8)

Conditions	Yield
In diethyl ether at -78 - 25℃;	100%

para-methylphenylmagnesium bromide (4294-57-9) + tert-butyl 2-phenyldiazene-1-carboxylate (92491-22-0) → N'-phenyl-N'-p-tolyl-hydrazinecarboxylic acid tert-butyl ester

Conditions	Yield
In tetrahydrofuran at -100℃;	100%

2-chloropyridine (109-09-1) + para-methylphenylmagnesium bromide (4294-57-9) → 2-(4-methylphenyl)pyridine (4467-06-5)

Conditions	Yield
With C32H41N12Ni2O(3+)*3F6P(1-) In tetrahydrofuran at 25℃; for 5h; Inert atmosphere; Schlenk technique;	100%
With N-heterocyclic carbene-based nickel(II) complex In tetrahydrofuran at 20℃; for 12h; Kumada reaction;	99%
With chloro(1,3-bis(pyridin-2-ylmethyl)imidazolylidene)nickel(II) hexafluorophosphate In tetrahydrofuran at 20℃; for 12h; Kumada-Corriu coupling reaction; Inert atmosphere;	99%

triphenyltin chloride (639-58-7) + para-methylphenylmagnesium bromide (4294-57-9) → triphenyl(p-tolyl)tin (15807-28-0)

Conditions	Yield
In diethyl ether	100%
In tetrahydrofuran byproducts: MgBrCl; dropwise addn. of Mg-compd. to Sn-compd, refluxed for 5 h, hydrolysed with HCl; evapd., filtered, dried, extd. (toluene), recrystd. (EtOH/toluene); elem. anal.;	55%

10-chlorophenothiabismine 5,5-dioxide (143674-29-7) + para-methylphenylmagnesium bromide (4294-57-9) → 10-(4'-methylphenyl)phenothiabismine 5,5-dioxide (143674-28-6)

Conditions	Yield
With ethylacetat In tetrahydrofuran (under Ar); addn. of 4-methylphenylmagnesium bromide in THF to 10-chlorophenothiabismine in THF, stirring for 10 min at room temp.; extn., sepn. of organic layer, drying, concg. under reduced pressure, recrystn. from MeOH-C6H6 (5:1), elem.anal.;	100%

3α-hydroxy-4α,4aα,7α,7aα-dihydronepetalactone (77714-57-9) + para-methylphenylmagnesium bromide (4294-57-9) → (3R,4R,4aR,7S,7aR)-4,7-dimethyl-3-(4-methylphenyl)hexahydrocyclopenta[c]pyran-1(3H)-one

Conditions	Yield
Stage #1: 3α-hydroxy-4α,4aα,7α,7aα-dihydronepetalactone With potassium hydride In tetrahydrofuran; hexane at 0℃; for 0.333333h; Stage #2: para-methylphenylmagnesium bromide In tetrahydrofuran; hexane at 0 - 20℃; for 1h;	100%

P,P-diphenyl-N-(phenyl(o-tolyl)methylene)phosphinic amide + para-methylphenylmagnesium bromide (4294-57-9) → P,P-diphenyl-N-(phenyl(o-tolyl)(p-tolyl)methyl)phosphinic amide

Conditions	Yield
In diethyl ether; n-heptane; toluene at 20℃; Inert atmosphere; Schlenk technique;	100%

trans geranyl acetone (3796-70-1) + para-methylphenylmagnesium bromide (4294-57-9) → E-6,10-dimethyl-2-hydroxy-2-(p-tolyl)-5,9-undecadiene (70026-33-4)

Conditions	Yield
In diethyl ether at 20℃;	100%

2,4,6-tris(phenyltelluro)-1,3,5-triazine (142312-17-2) + para-methylphenylmagnesium bromide (4294-57-9) → 2,4,6-tris(p-tolyl)-1,3,5-triazine (6726-45-0)

Conditions	Yield
With bis(triphenylphosphine)nickel(II) chloride In tetrahydrofuran for 8h; Heating;	99%

4-chloromethoxybenzene (623-12-1) + para-methylphenylmagnesium bromide (4294-57-9) → 4-(4-tolyl)anisole (53040-92-9)

Conditions	Yield
With tris(dibenzylideneacetone)dipalladium (0); N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene hydrochloride In tetrahydrofuran; 1,4-dioxane at 80℃; for 3h; Arylation;	99%
With N-heterocyclic carbene-based nickel(II) complex In tetrahydrofuran at 20℃; for 12h; Kumada reaction;	99%
With iron(II) triflate; 1,3-bis(2,4,6-trimethylphenyl)-4,5,6,7-tetrahydro-1H-1,3-diazepinium bromide; sodium t-butanolate In tetrahydrofuran at 60℃; for 16h; Kumada Cross-Coupling; Sealed tube; Inert atmosphere;	99%

δ-chlorovaleronitrile (6280-87-1) + para-methylphenylmagnesium bromide (4294-57-9) → 5-(p-tolyl)pentanenitrile (79593-79-6)

Conditions	Yield
With 1-methyl-pyrrolidin-2-one; palladium diacetate; tricyclohexylphosphine In tetrahydrofuran at 20℃; for 20h; Kumada coupling;	99%
With 1,3-bis(mesityl)imidazolium chloride; palladium diacetate In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 20℃; for 1h; Kumada reaction;	93%

isobutyryl chloride (513-36-0) + para-methylphenylmagnesium bromide (4294-57-9) → 1-methyl-4-(2-methylpropyl)-benzene (5161-04-6)

Conditions	Yield
With 1,3-bis(mesityl)imidazolium chloride; palladium diacetate In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 20℃; for 1h; Kumada reaction;	99%

1-bromocyclohexane (108-85-0) + para-methylphenylmagnesium bromide (4294-57-9) → 1-cyclohexyl-4-methylbenzene (4501-36-4)

Conditions	Yield
With C34H51N2O2(1+)*Cl4Fe(1-) In diethyl ether Concentration; Reagent/catalyst; Grignard Reaction;	99%
With N,N,N,N,-tetramethylethylenediamine; iron(III) chloride In tetrahydrofuran at 25℃; for 0.5h;	96%
With N,N,N,N,-tetramethylethylenediamine; iron(III) chloride In tetrahydrofuran at 25℃;	96%

fluorobenzene (462-06-6) + para-methylphenylmagnesium bromide (4294-57-9) → 4-Methylbiphenyl (644-08-6)

Conditions	Yield
With C35H31BrN4NiP In tetrahydrofuran at 25℃; for 24h; Schlenk technique; Inert atmosphere;	99%
With supramolecular ensemble of HP-T with Au-Fe3O4 nanoparticles; air In tetrahydrofuran; water at 20℃; for 3h; Kumada Cross-Coupling; Irradiation;	60%
1,3-bis[(diphenylphosphino)propane]dichloronickel(II) In tetrahydrofuran at 20℃; for 24h;	92 % Chromat.

N,N-diethyl phenyl O-sulfamate (1015-49-2) + para-methylphenylmagnesium bromide (4294-57-9) → 4-Methylbiphenyl (644-08-6)

Conditions	Yield
NiClCpIMes In diethyl ether at 40℃; for 24h; Grignard cross-coupling reaction;	99%

1-fluoro-4-methoxybenzene (459-60-9) + para-methylphenylmagnesium bromide (4294-57-9) → 4-(4-tolyl)anisole (53040-92-9)

Conditions	Yield
With C35H31BrN4NiP In tetrahydrofuran at 25℃; for 24h; Concentration; Schlenk technique; Inert atmosphere;	99%
With 1-[2-(diphenylphosphino)phenyl]ethanol; bis(acetylacetonate)nickel(II) In diethyl ether at 20℃; for 12h;	97%
With C26H24ClN2NiP*0.1C7H8 In toluene at 25℃; for 24h; Reagent/catalyst; Solvent; Kumada Cross-Coupling; Schlenk technique; Inert atmosphere;	90%

iodobenzene (591-50-4) + para-methylphenylmagnesium bromide (4294-57-9) → 4-Methylbiphenyl (644-08-6)

Conditions	Yield
amido pincer complex of nickel chloride catalyst In toluene at 20℃; for 12h; Kumada cross-coupling reaction;	99%
[Ni-(o-MeC6H4){2-{OC(Ph)2CH2}-6-(3,5-Me2C3HN2)C5H3N}] In tetrahydrofuran; toluene for 12h; Kumada reaction; Heating;	99%
With supramolecular ensemble of HP-T with Au-Fe3O4 nanoparticles; air In tetrahydrofuran; water at 20℃; for 0.333333h; Kumada Cross-Coupling; Irradiation;	87%

para-iodoanisole (696-62-8) + para-methylphenylmagnesium bromide (4294-57-9) → 4-(4-tolyl)anisole (53040-92-9)

Conditions	Yield
amido pincer complex of nickel chloride catalyst In toluene at 20℃; for 12h; Kumada cross-coupling reaction;	99%
With self-assembled multilayer nickel nanoparticle catalyst - sulfur-modified gold-supported Ni NPs (SANi) In tetrahydrofuran at 75℃; for 3h; Kumada Cross-Coupling; Inert atmosphere;	95%
[Ni(1-C10H7){2-{OC(Ph)2CH2}-6-(3,5-Me2C3HN2)C5H3N}] In tetrahydrofuran; toluene for 12h; Kumada reaction; Heating;	91%
With supramolecular ensemble of HP-T with Au-Fe3O4 nanoparticles; air In tetrahydrofuran; water at 20℃; for 0.333333h; Kumada Cross-Coupling; Irradiation;	89%

chlorobenzene (108-90-7) + para-methylphenylmagnesium bromide (4294-57-9) → 4-Methylbiphenyl (644-08-6)

Conditions	Yield
amido pincer complex of nickel chloride catalyst In tetrahydrofuran at 20℃; for 24h; Kumada cross-coupling reaction;	99%
With ((C6H4)(OPPh2)(NCHPhPPh2))NiCl In tetrahydrofuran at 25℃; for 24h; Kumada cross-coupling; Inert atmosphere;	99%
With Fe2(OtBu)6; sodium t-butanolate; 1,3-bis[(2,6-diisopropyl)phenyl]imidazolinium chloride In tetrahydrofuran at 80℃; for 16h; Catalytic behavior; Reagent/catalyst; Time; Kumada Cross-Coupling; Glovebox; Inert atmosphere;	99%

bromobenzene (108-86-1) + para-methylphenylmagnesium bromide (4294-57-9) → 4-Methylbiphenyl (644-08-6)

Conditions	Yield
[Pd(Cl){2-{OC(Ph)=CH}-6-(3,5-Me2C3HN2)C5H3N}] In tetrahydrofuran; toluene for 6h; Kumada reaction; Heating;	99%
With C16H16Cl2CoN8(1+)*F6P(1-) In tetrahydrofuran at 20℃; for 2h; Kumada-Corriu cross-coupling;	96%
With [1,3-bis(2,6-diisopropylphenyl)-imidazolium][Ni(PPh3)Cl3] In tetrahydrofuran at 30℃; for 1h; Kumada Cross-Coupling; Schlenk technique; Inert atmosphere;	96%

para-methylphenylmagnesium bromide (4294-57-9) + N,N-dimethyl-N-[2-(5,6,7,8-tetrahydronaphthalen-2-yloxy)ethyl]amine → 6-(4-methylphenyl)-1,2,3,4-tetrahydronaphthalene

Conditions	Yield
With tricyclohexylphosphine; bis(tricyclohexylphosphine)nickel(II) dichloride In formaldehyde diethyl acetal at 20 - 95℃; for 15h;	99%

bromobenzene (108-86-1) + para-methylphenylmagnesium bromide (4294-57-9) → (4,4'-dimethyl-1,1'-biphenyl) (613-33-2) + 4-Methylbiphenyl (644-08-6)

Conditions	Yield
With CoF2*4H2O; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride In tetrahydrofuran at 60℃; for 3h; Inert atmosphere;	A 7% B 99%
phenylnickel N-Bu-6-[1-(2,6-(Me)2PhN)ethyl]picolinamide In tetrahydrofuran; toluene at 20℃; for 24h;
With (N-(dimethylaminoethyl)-2-diphenylphosphinoaniline(-1H))NiCl In tetrahydrofuran at 25℃; for 12h; Kumada coupling reaction; Inert atmosphere;	A 32 %Chromat. B 63 %Chromat.

chlorobenzene (108-90-7) + para-methylphenylmagnesium bromide (4294-57-9) → (4,4'-dimethyl-1,1'-biphenyl) (613-33-2) + 4-Methylbiphenyl (644-08-6)

Conditions	Yield
With C68H72Cl2N6NiP2 In diethyl ether at 25℃; for 12h; Kumada coupling reaction; Inert atmosphere;	A n/a B 99%
With FeF3*H2O; tricyclohexylphosphine In tetrahydrofuran at 20 - 60℃; for 24h; Inert atmosphere;	A 4% B 5%
(1-naphthyl)Ni N-Bu-6-[1-(2,6-(i-Pr)2PhN)ethyl]picolinamide In tetrahydrofuran; toluene at 20℃; for 24h;

2-chloropyrimidine (1722-12-9) + para-methylphenylmagnesium bromide (4294-57-9) → 2-p-tolyl-pyrimidine (77232-13-4)

Conditions	Yield
With N-heterocyclic carbene-based nickel(II) complex In tetrahydrofuran at 20℃; for 12h; Kumada reaction;	99%
With chloro(1,3-bis(pyridin-2-ylmethyl)imidazolylidene)nickel(II) hexafluorophosphate In tetrahydrofuran at 20℃; for 12h; Kumada-Corriu coupling reaction; Inert atmosphere;	99%
With C16H16Cl2CoN8(1+)*F6P(1-) In tetrahydrofuran at 20℃; for 2h; Kumada-Corriu cross-coupling;	97%
With (IPr)Ni(π-allyl)Cl In tetrahydrofuran at 20℃; for 24h; Kumada Cross-Coupling; Inert atmosphere;	74%
With [Ni(1-(1-ethyl-benzimidazol-2-ylmethyl)-3-mesitylimidazolin-2-ylidene)2][Cl]2; sodium acetate In tetrahydrofuran at 20℃; Kumada-Corriu coupling reaction; Inert atmosphere;

4-Cyanochlorobenzene (623-03-0) + para-methylphenylmagnesium bromide (4294-57-9) → p-(p-tolyl)benzonitrile (50670-50-3)

Conditions	Yield
With ((C6H4)(OPPh2)(NCHPhPPh2))NiCl In tetrahydrofuran at 25℃; for 12h; Kumada cross-coupling; Inert atmosphere;	99%
With C35H31BrN4NiP In tetrahydrofuran at 25℃; for 14.5h; Schlenk technique; Inert atmosphere;	97%
With N-heterocyclic carbene-based nickel(II) complex In tetrahydrofuran at 20℃; for 12h; Kumada reaction;	84%

2,6-dichloropyridine (2402-78-0) + para-methylphenylmagnesium bromide (4294-57-9) → 2,6-di-p-tolylpyridine (14435-88-2)

Conditions	Yield
With chloro(1,3-bis(pyridin-2-ylmethyl)imidazolylidene)nickel(II) hexafluorophosphate In tetrahydrofuran at 20℃; for 12h; Kumada-Corriu coupling reaction; Inert atmosphere;	99%
With N-heterocyclic carbene-based nickel(II) complex In tetrahydrofuran at 20℃; for 12h; Kumada reaction;	95%

para-dichlorobenzene (106-46-7) + para-methylphenylmagnesium bromide (4294-57-9) → 1,4-bis(p-tolyl)benzene (97295-31-3)

Conditions	Yield
With C36H32ClN4NiP In tetrahydrofuran at 70℃; for 20h; Reagent/catalyst; Kumada Cross-Coupling; Schlenk technique; Inert atmosphere;	99%
With N-heterocyclic carbene-based nickel(II) complex In tetrahydrofuran at 20℃; for 12h; Kumada reaction;	89%
With C20H23BrN4Ni In tetrahydrofuran at 25℃; for 24h; Kumada Cross-Coupling; Inert atmosphere;	89%

Upstream product

• 60-29-7 diethyl ether 
• 537-64-4 bis(p-tolyl)mercury 
• 106-38-7 para-bromotoluene 
• 179088-99-4 5-(2-chlorophenyl)-2-(4-methoxybenzyl)tetrazole 
• 3264-82-2 nickel(II) acetylacetonate 
• 13482-64-9 bis(chloromethyl)phosphinic chloride 
• 7439-95-4 magnesium 

Downstream Products

• 699-02-5 4-Methylphenethyl alcohol 
• 75488-44-7 2-[1-(4-methylphenyl)ethenyl]thiophene 
• 100371-92-4 5-(1-methyl-1-p-tolyl-ethyl)-2-thioxo-thiazolidin-4-one 
• 5467-89-0 bis(4-methylphenyl)-2-pyridylmethanol 
• 101868-40-0 (4-chloro-phenyl)-[4]pyridyl-p-tolyl-methanol 
• 42156-84-3 8-p-toluoyl-[1]naphthoic acid 
• 114001-55-7 2-(4-ethoxy-phenyl)-3-p-tolyl-inden-1-one 
• 113113-85-2 5-(2-methoxy-4'-methyl-benzhydryl)-3-phenyl-thiazolidine-2,4-dione 
• 100476-12-8 (2-chlorophenyl)(p-tolyl)methanol 
• 5895-68-1 bis-(4,4'-dimethyl-benzhydrylidene)-hydrazine 
• 21034-34-4 (±)-5-(4-methylphenyl)-γ-valerolactone 
• 129919-70-6 1,3-diphenyl-3-(4-methylphenyl)-1-propanone 
• 17881-63-9 chlorodimethyl(4-methylphenyl)silane 
• 3333-13-9 p-allyltoluene 

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