Palladium-catalyzed cross-methylation of haloarenes possessing active hydrogen atoms by intramolecularly stabilized dimethylindium and dimethylaluminum reagents

Nimer Jaber; Dmitri Gelman; Herbert Schumann; Sebastian Dechert; Jochanan Blum

doi:10.1002/1099-0690(200205)2002:10<1628::aid-ejoc1628>3.0.co;2-c

Palladium-catalyzed cross-methylation of haloarenes possessing active hydrogen atoms by intramolecularly stabilized dimethylindium and dimethylaluminum reagents

Nimer Jaber, Dmitri Gelman, Herbert Schumann, Sebastian Dechert, Jochanan Blum^*

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

34 Scopus citations

Abstract

While the intramolecularly stabilized aluminum complex [(CH₃)₂AlOCH₂CH₂ N(CH₃)₂]₂ (2a) reacts readily with 4-bromophenol to give methane and [(4-BrC₆H₄O)₂Al-OCH₂ CH₂N(CH₃)₂]₂ (7), the demethylation of the analogous indium complex [(CH₃)₂InOCH₂CH₂ N(CH₃)₂]₂ 2c is very slow. This inertness of 2c enables it to cross-methylate bromophenols and other bromoarenes with active hydrogen atoms in the presence of soluble palladium phosphane catalysts. The cross-methylation by 2c can be carried out under an ambient atmosphere. The ring-bound bromine atoms in 7 are replaced by CH₃ groups when treated with an excess of the methylation reagent 2a, and the resulting aluminum cresolate liberates 4-methylphenol upon hydrolysis.

Original language	English
Pages (from-to)	1628-1632
Number of pages	5
Journal	European Journal of Organic Chemistry
Issue number	10
DOIs	https://doi.org/10.1002/1099-0690(200205)2002:10<1628::aid-ejoc1628>3.0.co;2-c
State	Published - 2002

Keywords

Aluminum
Cross coupling
Indium
N,O ligands

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10.1002/1099-0690(200205)2002:10<1628::aid-ejoc1628>3.0.co;2-c

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title = "Palladium-catalyzed cross-methylation of haloarenes possessing active hydrogen atoms by intramolecularly stabilized dimethylindium and dimethylaluminum reagents",

abstract = "While the intramolecularly stabilized aluminum complex [(CH3)2AlOCH2CH2 N(CH3)2]2 (2a) reacts readily with 4-bromophenol to give methane and [(4-BrC6H4O)2Al-OCH2 CH2N(CH3)2]2 (7), the demethylation of the analogous indium complex [(CH3)2InOCH2CH2 N(CH3)2]2 2c is very slow. This inertness of 2c enables it to cross-methylate bromophenols and other bromoarenes with active hydrogen atoms in the presence of soluble palladium phosphane catalysts. The cross-methylation by 2c can be carried out under an ambient atmosphere. The ring-bound bromine atoms in 7 are replaced by CH3 groups when treated with an excess of the methylation reagent 2a, and the resulting aluminum cresolate liberates 4-methylphenol upon hydrolysis.",

keywords = "Aluminum, Cross coupling, Indium, N,O ligands",

author = "Nimer Jaber and Dmitri Gelman and Herbert Schumann and Sebastian Dechert and Jochanan Blum",

year = "2002",

doi = "10.1002/1099-0690(200205)2002:10<1628::aid-ejoc1628>3.0.co;2-c",

language = "אנגלית",

pages = "1628--1632",

journal = "European Journal of Organic Chemistry",

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publisher = "Wiley-VCH Verlag",

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T1 - Palladium-catalyzed cross-methylation of haloarenes possessing active hydrogen atoms by intramolecularly stabilized dimethylindium and dimethylaluminum reagents

AU - Jaber, Nimer

AU - Gelman, Dmitri

AU - Schumann, Herbert

AU - Dechert, Sebastian

AU - Blum, Jochanan

PY - 2002

Y1 - 2002

N2 - While the intramolecularly stabilized aluminum complex [(CH3)2AlOCH2CH2 N(CH3)2]2 (2a) reacts readily with 4-bromophenol to give methane and [(4-BrC6H4O)2Al-OCH2 CH2N(CH3)2]2 (7), the demethylation of the analogous indium complex [(CH3)2InOCH2CH2 N(CH3)2]2 2c is very slow. This inertness of 2c enables it to cross-methylate bromophenols and other bromoarenes with active hydrogen atoms in the presence of soluble palladium phosphane catalysts. The cross-methylation by 2c can be carried out under an ambient atmosphere. The ring-bound bromine atoms in 7 are replaced by CH3 groups when treated with an excess of the methylation reagent 2a, and the resulting aluminum cresolate liberates 4-methylphenol upon hydrolysis.

AB - While the intramolecularly stabilized aluminum complex [(CH3)2AlOCH2CH2 N(CH3)2]2 (2a) reacts readily with 4-bromophenol to give methane and [(4-BrC6H4O)2Al-OCH2 CH2N(CH3)2]2 (7), the demethylation of the analogous indium complex [(CH3)2InOCH2CH2 N(CH3)2]2 2c is very slow. This inertness of 2c enables it to cross-methylate bromophenols and other bromoarenes with active hydrogen atoms in the presence of soluble palladium phosphane catalysts. The cross-methylation by 2c can be carried out under an ambient atmosphere. The ring-bound bromine atoms in 7 are replaced by CH3 groups when treated with an excess of the methylation reagent 2a, and the resulting aluminum cresolate liberates 4-methylphenol upon hydrolysis.

KW - Aluminum

KW - Cross coupling

KW - Indium

KW - N,O ligands

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AN - SCOPUS:0036105814

SN - 1434-193X

SP - 1628

EP - 1632

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 10

ER -

Palladium-catalyzed cross-methylation of haloarenes possessing active hydrogen atoms by intramolecularly stabilized dimethylindium and dimethylaluminum reagents

Abstract

Keywords

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