Ruthenium catalyzed synthesis of secondary or tertiary amines from amines and alcohols

Murahashi, Shun‐Ichi; Kondo, Kaoru; Hakata, Toshiyuki

doi:10.1016/s0040-4039(00)86792-1

Cited by 174 publications

(61 citation statements)

References 7 publications

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“…To demonstrate the power of the new C-N bond formation, we applied the Fe-catalyzed direct amine alkylation as a key connection step in the synthesis of the N-arylpiperazine drug Piribedil (12) (Fig. 6a), a dopamine antagonist used in the treatment of Parkinson's disease 11,31 .…”

Section: Heterocycle Formation With Various Benzylamines and Diolsmentioning

confidence: 99%

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Iron catalysed direct alkylation of amines with alcohols

2014

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The selective conversion of carbon-oxygen bonds into carbon-nitrogen bonds to form amines is one of the most important chemical transformations for the production of bulk and fine chemicals and pharma intermediates. An attractive atom-economic way of carrying out such C-N bond formations is the direct N-alkylation of simple amines with alcohols by the borrowing hydrogen strategy. Recently, transition metal complexes based on precious metals have emerged as suitable catalysts for this transformation; however, the crucial change towards the use of abundant, inexpensive and environmentally friendly metals, in particular iron, has not yet been accomplished. Here we describe the homogeneous, iron-catalysed, direct alkylation of amines with alcohols. The scope of this new methodology includes the monoalkylation of anilines and benzyl amines with a wide range of alcohols, and the use of diols in the formation of five, six-and seven-membered nitrogen heterocycles, which are privileged structures in numerous pharmaceuticals.

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Section: Heterocycle Formation With Various Benzylamines and Diolsmentioning

confidence: 99%

“…A number of transition metal complexes have proven effective in this catalytic C-N bond formation, in particular, those based on ruthenium [10][11][12] and iridium 13 . These and related methodologies have been extensively reviewed 1,3,4,[14][15][16] .…”

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confidence: 99%

Iron catalysed direct alkylation of amines with alcohols

2014

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“…Thus, the reaction between amines and alcohols has been investigated in detail, particularly using homogeneous catalysts based on late transition metals; [1Ϫ12] those based on ruthenium have been the most widely investigated, including the ruthenium() complexes [RuCl 2 (PPh 3 ) 3 ], [1,3,5Ϫ12] [RuH 2 (PPh 3 ) 4 ], [2,4,5Ϫ7] [RuHCl(CO)(PPh 3 ) 3 ], [5,11] [RuBr 2 -(PPh 3 ) 3 ], [6] [RuHCl(PPh 3 ) 3 ], [6] [RuH 2 {P(OEt) 3 } 4 ], [7] [RuCl 2 (CO) 2 (PPh 3 ) 2 ], [8] [RuCl 2 (PϪN) 2 ], [8] (PϪN ϭ o-diphenylphosphanyl-N,N-dimethylaniline) [RuH 2 (CO)-(PPh 3 ) 3 ], [11] [{RuCl 2 (η 5 -C 5 Me 5 )} 2 ], [11] as well as those bearing terdentate NPN or NNЈN type ligands, [12] the ruthenium(0) derivatives [Ru(CO) 3 (PPh 3 ) 2 ], [5] [Ru 3 -(CO) 12 ], [11] and [Ru(cot)(cod)], [11] and, finally, ''in situ'' generated systems [RuCl 3 /phosphane [6,7] or RuCl 3 /P(OR) 3 [6,7] ] exhibit catalytic activity in the N-alkylation of amines by alcohols. Although the reaction is commonly performed in an autoclave at 120Ϫ215°C, long reaction times are often required to obtain high yields of products.…”

Section: Introductionmentioning

confidence: 99%

Cyclopentadienyl Ru^II Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

et al. 2004

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The ruthenium(II) half-sandwich complex [RuCl(η 5 -C 5 H 5 )(PPh 3 ) 2 ] (1) catalyses the reaction between methanol and alkylamines RNH 2 or R 1 R 2 NH to afford RN(CH 3 ) 2 and R 1 R 2 NCH 3 products, respectively. The reaction is quantitative and generally fast, at the methanol reflux temperature, for a wide spectrum of substrates. Starting from primary amines, the stepwise formation of RN=CH 2 , RNHCH 3 , and

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“…RuH 2 A C H T U N G T R E N N U N G (PPh 3 ) 4 has also been used to catalyse similar cyclisation reactions, as well as cyclisation/alkylation reactions such as the conversion of amino alcohol 31 and alcohol 32 into the cyclic product 33 (Scheme 11). [34] …”

Section: Cyclisation Of Amino Alcoholsmentioning

confidence: 99%

Borrowing Hydrogen in the Activation of Alcohols

2007

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Alcohols can be temporarily converted into carbonyl compounds by the metal-catalysed removal of hydrogen. The carbonyl compounds are reactive in a wider range of transformations than the precursor alcohols and can react in situ to give imines, alkenes, and a-functionalised carbonyl compounds. The metal catalyst, which had borrowed the hydrogen, then returns it to the transformed carbonyl compound, leading to an overall process in which alcohols can be converted into amines, compounds containing C À C bonds and b-functionalised alcohols.

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Ruthenium catalyzed synthesis of secondary or tertiary amines from amines and alcohols

Cited by 174 publications

References 7 publications

Iron catalysed direct alkylation of amines with alcohols

Iron catalysed direct alkylation of amines with alcohols

Cyclopentadienyl Ru^II Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

Borrowing Hydrogen in the Activation of Alcohols

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Ruthenium catalyzed synthesis of secondary or tertiary amines from amines and alcohols

Cited by 174 publications

References 7 publications

Iron catalysed direct alkylation of amines with alcohols

Iron catalysed direct alkylation of amines with alcohols

Cyclopentadienyl RuII Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol

Borrowing Hydrogen in the Activation of Alcohols

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Cyclopentadienyl Ru^II Complexes as Highly Efficient Catalysts for the N‐Methylation of Alkylamines by Methanol