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Methylation of amines is a fundamental and commonly used reaction in organic synthesis. Many methods are known including various reductive methylations using formaldehyde, formic acid, or carbon dioxide in the presence of reductants. However, several of these methods suffer from limited substrate scope and chemoselectivity because of the different nucleophilicities of substrates. In this respect, the combination of carbonates and hydrosilanes is a valuable methylation source in the presence of Pt-based catalysts. This highly tunable method allows for methylation of both aromatic and aliphatic amines, and chemoselective methylation of aminoalcohols and diamines. Notably, the in situ-formed catalyst can also be used for the reduction of carbonates to methanol at room temperature. Mechanistic insights on intermediates formed during the reaction pathway were obtained by using ESI mass spectrometry. [ABSTRACT FROM AUTHOR]

Formation of C-C bonds from CO2 is a much sought after reaction in organic synthesis. To date, other than C-H carboxylations using stoichiometric amounts of metals, base, or organometallic reagents, little is known about C-C bond formation. In fact, to the best of our knowledge no catalytic methylation of C-H bonds using CO2 and H2 has been reported. Described herein is the combination of CO2 and H2 for efficient methylation of carbon nucleophiles such as indoles, pyrroles, and electron-rich arenes. Comparison experiments which employ paraformaldehyde show similar reactivity for the CO2/H2 system. [ABSTRACT FROM AUTHOR]

Formation of C-C bonds from CO2 is a much sought after reaction in organic synthesis. To date, other than C-H carboxylations using stoichiometric amounts of metals, base, or organometallic reagents, little is known about C-C bond formation. In fact, to the best of our knowledge no catalytic methylation of C-H bonds using CO2 and H2 has been reported. Described herein is the combination of CO2 and H2 for efficient methylation of carbon nucleophiles such as indoles, pyrroles, and electron-rich arenes. Comparison experiments which employ paraformaldehyde show similar reactivity for the CO2/H2 system. [ABSTRACT FROM AUTHOR]

The authors focus on the methylation of amines with carbon dioxide and hydrogen molecule (H2). They mention that two catalysts formed from ruthenium acetylacetonate [Ru(acac)3] and 1,1,1-tris(diphenylphosphinomethyl) ethane, enabled the conversion of carbon dioxide and carboxylic acid derivatives into N,N-dimethylaniline and N-methylaniline. They mention that methylation reaction with formamide and methanol formed intermediates, which then reduced to a methylated product.

The authors focus on the methylation of amines with carbon dioxide and hydrogen molecule (H2). They mention that two catalysts formed from ruthenium acetylacetonate [Ru(acac)3] and 1,1,1-tris(diphenylphosphinomethyl) ethane, enabled the conversion of carbon dioxide and carboxylic acid derivatives into N,N-dimethylaniline and N-methylaniline. They mention that methylation reaction with formamide and methanol formed intermediates, which then reduced to a methylated product.

Kohlendioxid kann zur selektiven reduktiven Methylierung sekundärer und primärer aromatischer und aliphatischer Amine verwendet werden. Vielfältige tertiäre Amine werden durch Einwirkung von CO2 und käuflichen Silanen in hohen Ausbeuten erhalten. Die Katalysereaktion toleriert Nitril ‐ , Olefin ‐ , Ether ‐ , Ester ‐ und Hydroxygruppen in den Substraten. [ABSTRACT FROM AUTHOR]

A diagram of the chemical structure is presented which shows reductive methylation of amines using carbonates.

The article presents chemical equations related to the article "Selective Methylation of Amines with Carbon Dioxide and H2" by Y Li and others published in the periodical "Angewandte Chemie International Edition" in 2013.

The article presents chemical equations related to the article "A General Catalytic Methylation of Amines Using Carbon Dioxide" by Y. Li and colleagues, published in the periodical "Angewandte Chemie International Edition" in 2013.