A Simple Catalyst for the Efficient Benzylation of Arenes by Using Alcohols, Ethers, Styrenes, Aldehydes, or Ketones

Prades, Amparo; Corberán, Rosa; Poyatos, Macarena; Peris, Eduardo

doi:10.1002/chem.200802740

Cited by 84 publications

(42 citation statements)

References 37 publications

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“…This is an important result for synthetic applications, because Friedel-Crafts benzylations of toluene afford only mixtures of ortho and para-isomers. [3,14] On the other hand, an allyl group was not tolerated in the presence of chlorosulfonic acid, and only polymeric material was isolated (entry 2). The alcohol 2 u reacted to a single product, but no decarbonylation was observed and an interesting spirolactone 4 u was isolated in 92 % yield [Eq.…”

Section: Entrymentioning

confidence: 99%

“…

[a]

IntroductionArene functionalizations are of current interest in organic chemistry, and many industrial processes are based on such transformations.[1] The formation of C À C bonds represents one of the most important reactions, and the traditional Friedel-Crafts alkylation, [2] especially in combination with new catalysts, [3] is often applied, although the moderate regioselectivities and bis-alkylations are disadvantageous. Modern methodologies such as Heck reactions or Stille and Suzuki couplings proceed in the presence of palladium catalysts under mild conditions and afford exclusively one regioisomer.

[4] However, the synthesis of the aromatic precursors is often tedious, and many C À C couplings are limited to sp 2 and sp centers due to competing b-hydride eliminations.

…”

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confidence: 99%

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Regioselective Arene Functionalization: Simple Substitution of Carboxylate by Alkyl Groups

Krüger

Vorndran

Linker

2009

Chemistry A European J

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Arenes with various alkyl side-chains were synthesized in high yields and excellent regioselectivities. Starting from toluic and naphthoic acids, the carboxylate group was conveniently substituted by alkyl halides by Birch reduction and subsequent decarbonylation. The method is characterized by inexpensive starting materials and reagents, and methylation of arenes was realized. Besides simple alkyl substituents, the scope of arene functionalization was extended by benzyl, fluoro, amino, and ester groups. We were able to control the alkylation of 1-naphthoic acid during Birch reduction by the addition of tert-butanol. This allowed the regioselective synthesis of mono and bis-substituted naphthalenes from the same starting material.

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Section: Entrymentioning

confidence: 99%

“…

[a]

[4] However, the synthesis of the aromatic precursors is often tedious, and many C À C couplings are limited to sp 2 and sp centers due to competing b-hydride eliminations.

…”

mentioning

confidence: 99%

Regioselective Arene Functionalization: Simple Substitution of Carboxylate by Alkyl Groups

Krüger

Vorndran

Linker

2009

Chemistry A European J

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“…Next to the described procedures many related intermolecular FC-type alkylations with styrenes and activated double bonds have been developed using, for instance, InCl 3 /SiO 2 [11], Iodine [62], Ir(III) [51], AuCl 3 /AgSbF 6 [63], AuCl [64], and PtCl 2 [65]. …”

Section: Reviewmentioning

confidence: 99%

A review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis

Rueping¹,

Nachtsheim²

2010

Beilstein J. Org. Chem.

604

353

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SummaryThe development of efficient Friedel–Crafts alkylations of arenes and heteroarenes using only catalytic amounts of a Lewis acid has gained much attention over the last decade. The new catalytic approaches described in this review are favoured over classical Friedel–Crafts conditions as benzyl-, propargyl- and allyl alcohols, or styrenes, can be used instead of toxic benzyl halides. Additionally, only low catalyst loadings are needed to provide a wide range of products. Following a short introduction about the origin and classical definition of the Friedel–Crafts reaction, the review will describe the different environmentally benign substrates which can be applied today as an approach towards greener processes. Additionally, the first diastereoselective and enantioselective Friedel–Crafts-type alkylations will be highlighted.

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“…In all the cases, alkylation went smoothly to furnish the expected product/s in high yields (Table 1, entries [14][15][16][17][18][19][20].…”

Section: Methodsmentioning

confidence: 99%

Microwave-Accelerated Alkylation of Arenes/Heteroarenes with Benzylic Alcohols Using Antimony(III) Chloride as Catalyst: Synthesis of O-Heterocycles

Shukla¹,

Choudhary²,

Nayak³

2011

Synlett

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An efficient protocol for alkylation of electron-rich arenes/heteroarenes with benzylic alcohols under microwave irradiation using antimony(III) chloride as catalyst has been developed. The mild reaction conditions, high yields, operational simplicity, and applicability to various substrates render the approach a useful route for the synthesis of diaryl/triarylalkane. In addition, a new route for the conversion of ortho-alkenylated phenols into functionalized O-heterocycles has been accomplished.

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A Simple Catalyst for the Efficient Benzylation of Arenes by Using Alcohols, Ethers, Styrenes, Aldehydes, or Ketones

Cited by 84 publications

References 37 publications

Regioselective Arene Functionalization: Simple Substitution of Carboxylate by Alkyl Groups

Regioselective Arene Functionalization: Simple Substitution of Carboxylate by Alkyl Groups

A review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis

Microwave-Accelerated Alkylation of Arenes/Heteroarenes with Benzylic Alcohols Using Antimony(III) Chloride as Catalyst: Synthesis of O-Heterocycles

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