Palladium-Catalyzed Etherification of Allyl Alcohols Using Phenols in the Presence of Titanium(IV) Isopropoxide

Satoh, Tetsuya; Ikeda, Masahiro; Miura, Masahiro; Nomura, Masakatsu

doi:10.1021/jo970534r

Cited by 115 publications

(42 citation statements)

References 25 publications

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“…From an environmental and atom-efficiency point of view it would be attractive to use allyl alcohol as the allyl donor, as only water is coproduced. However, the Pd systems for phenol allylation all use stoichiometric amounts of base [TiA C H T U N G T R E N N U N G (O-i-Pr) 4 ] to induce O-allylation, [5] or Lewis acid (BEt 3 ) to promote C-allylation. [6] With such Pd systems, electron-rich phenols such as 3,5-dimethoxyphenol and 1-naphthol were selectively C-allylated with allyl alcohol into 4-allyl-3,5-dimethoxyphenol and 2-allyl-1-naphthol, respectively, of which the latter does not require the use of a stoichiometric amount of base.…”

Section: Introductionmentioning

confidence: 99%

“…[6] With such Pd systems, electron-rich phenols such as 3,5-dimethoxyphenol and 1-naphthol were selectively C-allylated with allyl alcohol into 4-allyl-3,5-dimethoxyphenol and 2-allyl-1-naphthol, respectively, of which the latter does not require the use of a stoichiometric amount of base. [5,7] In one example, C-allylation of phenols in an aqueous environment is induced by adding large amounts of base to the system. [8] The yields in this system are very low.…”

Section: Introductionmentioning

confidence: 99%

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Cationic Ruthenium‐Cyclopentadienyl‐Diphosphine Complexes as Catalysts for the Allylation of Phenols with Allyl Alcohol; Relation between Structure and Catalytic Performance in O‐ vs. C‐Allylation

et al. 2009

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A new catalytic method has been investigated to obtain either O-or C-allylated phenolic products using allyl alcohol or diallyl ether as the allyl donor. With the use of new cationic rutheni-A C H T U N G T R E N N U N G um(II) complexes as catalyst, both reactions can be performed with good selectivity. Active cationic Ru(II) complexes, having cyclopentadienyl and bidentate phosphine ligands are generated from the corresponding Ru(II) chloride complexes with a silver salt. The structures of three novel (diphos-A C H T U N G T R E N N U N G phine)Ru(II)CpCl catalyst precursor complexes are reported. It appears that the structure of the bidentate ligand has a major influence on catalytic activity as well as chemoselectivity. In addition, a strong cocatalytic effect of small amounts of acid is revealed. Model experiments are described that have been used to build a reaction network that explains the origin and evolution in time of both O-allylated and C-allylated phenolic products. Some mechanistic implications of the observed structure vs. performance relation of the [(diphosphine)RuCp] + complexes and the cocatalytic role of added protons are discussed.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cationic Ruthenium‐Cyclopentadienyl‐Diphosphine Complexes as Catalysts for the Allylation of Phenols with Allyl Alcohol; Relation between Structure and Catalytic Performance in O‐ vs. C‐Allylation

et al. 2009

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“…30,31 The palladium catalyzed etherification of allylic alcohols with phenols is promoted by Ti(IV) isopropoxide, and formation of a transient allyl titanate leading to an 3-allylpalladium intermediate is supported by the formation of diallyl and diisopropyl ethers in the absence of a phenol. 32 Interestingly, we have successfully applied Pd-catalyzed O-alkylation of complex macrocyclic alcohols by allyl-tert-butylcarbonate. 33,34 Diaryl ethers, 9,35 aryl alkyl ethers 36 and enol ethers 37 can be synthesized by means of a palladium-catalyzed Buchwald-Hartwig reaction.…”

Section: Overview Of Traditional and Less Known Methodsmentioning

confidence: 99%

Ethers from esters; from exceptional transformation to synthetic method

Jakopović¹,

Kapić²,

Alihodžić³

et al. 2015

Arkivoc

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Most ether-bond forming reactions based on traditional methods or modifications thereof require strongly acidic or basic conditions and often harsh reaction conditions. Reduction of esters to ethers has been regarded as an impracticable method, generally affording alcohols as the principal products. Only recently, original, mostly catalytic methods for reduction of esters to ethers have been reported, which proceed under mild conditions and are compatible with many functional groups present in the substrate ester molecule. These reactions are considered as a valuable alternative to traditional methods, and specific protocols have been reported. An account of the progress in this synthetic methodology is given.

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“…Reductive elimination affords the allylated ketones, while β-hydrogen elimination produces the α,β-unsaturated ketones as the final products. Miura and co-workers employed Pd(OAc) 2 /PPh 3 and Ti(O i Pr) 4 catalysts in the allylic substitution reaction between allyl alcohol and phenols (Scheme 1.64) [82]. Without the addition of the Ti catalyst, the reaction was sluggish and only a low yield of the desired allyl phenyl ether was obtained.…”

Section: Reactions Promoted By a Combination Of Catalytic Amounts Of mentioning

confidence: 99%

Organic Synthesis with Bimetallic Systems

Kamijo

Yamamoto

2006

ChemInform

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Palladium-Catalyzed Etherification of Allyl Alcohols Using Phenols in the Presence of Titanium(IV) Isopropoxide

Cited by 115 publications

References 25 publications

Cationic Ruthenium‐Cyclopentadienyl‐Diphosphine Complexes as Catalysts for the Allylation of Phenols with Allyl Alcohol; Relation between Structure and Catalytic Performance in O‐ vs. C‐Allylation

Cationic Ruthenium‐Cyclopentadienyl‐Diphosphine Complexes as Catalysts for the Allylation of Phenols with Allyl Alcohol; Relation between Structure and Catalytic Performance in O‐ vs. C‐Allylation

Ethers from esters; from exceptional transformation to synthetic method

Organic Synthesis with Bimetallic Systems

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