Selective mono N-methylation of anilines with methanol catalyzed by rhenium complexes: An experimental and theoretical study

Wei, Duo; Sadek, Omar; Dorcet, Vincent; Roisnel, Thierry; Darcel, Christophe; Gras, Emmanuel; Clot, Eric; Sortais, Jean‐Baptiste

doi:10.1016/j.jcat.2018.08.008

Cited by 62 publications

(84 citation statements)

References 111 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[20] Nevertheless, to date, only three catalytic systemsa re reported for the synthesis of quinolines, two of which are using over-stoichiometric amounts of base. [24] Beller's group independently reported hydrogen auto-transfer and related dehydrogenative coupling reactions to form a-alkylated ketones and substituted pyrroles by using the same rhenium PN(H)P pincercomplex A. [22] Recently,w eh ave developed as eries of rheniumc omplexes with tridentate PN(H)P ligands (Scheme 1, A-E), which were efficiently employed in the hydrogenationo fc arbonyl derivatives [23] and the mono-N-methylation of anilinesw ith methanol as C1 source.…”

mentioning

confidence: 99%

“…Complexes A, B,a nd C showed excellent reactivity (Table 1, entries 1-3) at ac atalystl oading of 5mol %int oluene at 140 8Cfor 24 hint he presence of catalytic amountso ftBuOK (10 mol %), resulting in yields of 88, 8 7, and 90 %, respectively.N ot surprisingly, complexes D and E, bearingt he more sterically hindered PNP ligands, as well as the precursor Re(CO) 5 Br were not active (entries 4-6), whichi s in line with the reactivity already observed for the mono-Nmethylation of anilines. [24] The conditions of the reactionw ere furthero ptimized with complex C (1 mol %) at 150 8C. Various bases weret ested (entries 7-10) and tBuOK was shown to be the best candidate, resulting in 87 %y ield.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Quinolines Through Acceptorless Dehydrogenative Coupling Catalyzed by Rhenium PN(H)P Complexes

et al. 2019

Self Cite

View full text Add to dashboard Cite

Ap ractical and sustainable synthesis of substituted quinolines was achieved through the annulation of 2-aminobenzyl alcohol with various secondary alcohols, ketones,a ldehydes, or nitriles, under hydrogen-borrowing conditions. Under the catalysis of well-defined rhenium complexes bearing tridentate diphosphinoamino ligands, the reactionp roceeded efficiently (31 examples were isolated with yields up to 96 %) affording av arietyo f quinoline derivatives.

show abstract

mentioning

confidence: 99%

mentioning

confidence: 99%

Synthesis of Quinolines Through Acceptorless Dehydrogenative Coupling Catalyzed by Rhenium PN(H)P Complexes

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…Recently, the Sortais group reported a rhenium‐catalyzed selective mono N‐methylation of anilines with methanol . Catalyst 420 was selected, and the monomethylated products were obtained in good to excellent yields (Table ).…”

Section: Monomethylationmentioning

confidence: 99%

Recent Advances in Methylation: A Guide for Selecting Methylation Reagents

Chen

2018

Chemistry A European J

177

116

View full text Add to dashboard Cite

Methylation is a well‐known structural modification in organic and medicinal chemistry. This review summarizes recent advances in methylation by categorizing specific methylation reagents. The challenges of mono N‐methylation of aliphatic amines and N‐methylation of peptides are discussed. This review will be useful for chemists wanting to select the appropriate reagents for methylation chemistry. Based on the large diversity of methylation reagents and their wide scope, this review also broadens perspectives on which strategies to select for utilizing a particular methylation, resulting in an increased flexibility in synthetic route planning.

show abstract

“…realized the first homogenously Rh, Ir phosphine complexes‐catalyzed N ‐methylation of amines by methanol in 1981 . Since then, a few homogeneous Ru, Ir, Fe, Mn, and Co complexes have been further developed for the N ‐methylation of amines by methanol. However, these homogeneous catalytic systems cannot be reused, which seriously limited large‐scale industrial applications.…”

Section: N‐methylation Of Aniline With Methanol Catalyzed By Pd/c[a]mentioning

confidence: 99%

Selective N‐Monomethylation of Anilines with Methanol Catalyzed by Commercial Pd/C as an Efficient and Reusable Catalyst

et al. 2019

View full text Add to dashboard Cite

N-methylation of amines is one of the most important CÀ N bond-forming reactions and is widely utilized for the synthesis of numerous agrochemicals, drugs, natural products, and dyes. In this paper, the N-monomethylation of aniline derivatives using Pd/C catalyst and methanol as the methylation reagent was investigated. The N-monomethylation of various anilines was achieved with high activity and selectivity under relatively mild reaction conditions, and the yield of N-monomethyl anilines was over 90 %. Notably, the commercial, readily available, and inexpensive heterogeneous catalyst, Pd/C, could be easily recovered and reused more than five times with only a slight decrease in activity; gram-scale experiments were also successfully performed.

show abstract

Selective mono N-methylation of anilines with methanol catalyzed by rhenium complexes: An experimental and theoretical study

Cited by 62 publications

References 111 publications

Synthesis of Quinolines Through Acceptorless Dehydrogenative Coupling Catalyzed by Rhenium PN(H)P Complexes

Synthesis of Quinolines Through Acceptorless Dehydrogenative Coupling Catalyzed by Rhenium PN(H)P Complexes

Recent Advances in Methylation: A Guide for Selecting Methylation Reagents

Selective N‐Monomethylation of Anilines with Methanol Catalyzed by Commercial Pd/C as an Efficient and Reusable Catalyst

Contact Info

Product

Resources

About