Ruthenium-Catalyzed <i>N</i>-Alkylation of Amines and Sulfonamides Using Borrowing Hydrogen Methodology

Hamid, Malai Haniti S. A.; Allen, C. M. Van; Lamb, Gareth W.; Maxwell, Aoife C.; Maytum, Hannah C.; Watson, Andrew J. A.; Williams, Jonathan M. J.

doi:10.1021/ja807323a

Cited by 615 publications

(249 citation statements)

References 71 publications

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“…9 We therefore investigated the reaction of 19 with a range of cyclic alcohols, analysing for conversion by GC (Table 1). For catalyst A, cyclobutanol was found to be a markedly better substrate than higher homologues, while for catalyst B cyclopentanol performed best.…”

Section: Scheme 10 Borrowing Hydrogen Route To Piperazine 17mentioning

confidence: 99%

A Survey of the Borrowing Hydrogen Approach to the Synthesis of some Pharmaceutically Relevant Intermediates

Leonard

Blacker

Marsden

et al. 2015

Org. Process Res. Dev.

152

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RECEIVED DATE (to be automatically inserted after your manuscript is accepted if requiredaccording to the journal that you are submitting your paper to) 2 TOC AbstractCommercial reagents and literature conditions used to evaluate "Borrowing hydrogen" methodology for pharmaceutical intermediates. Yields are high for simple R/R', but challenges identified for typical pharma substrates. 3 AbstractThe use of the "borrowing hydrogen strategy" in the synthesis of a number of typical pharmaceutical intermediates has been investigated. The main aim of this work was to investigate the scope and limitations of current methodology using standard laboratory techniques in an industrial context. Some interesting and significant results were achieved across a diverse set of complex substrates; however several drawbacks with this approach were identified, such as the high loading, poor turnover and susceptibility to substrate inactivation of the catalysts. These are areas which are highlighted for future investigation and improvements.

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Section: Scheme 10 Borrowing Hydrogen Route To Piperazine 17mentioning

confidence: 99%

A Survey of the Borrowing Hydrogen Approach to the Synthesis of some Pharmaceutically Relevant Intermediates

Leonard

Blacker

Marsden

et al. 2015

Org. Process Res. Dev.

152

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“…Analysis of the sample was consistent with data reported in the literature. [20] In a stainless steel autoclave was placed 2-(dimethylamino)ethyl ethyl carbonate (300 mg, 1.86 mmol) with N-methylaniline (598 mg, 5.58 mmol) in 100 mL of acetonitrile at 180°C while stirring. The progress of the reaction was monitored by GC-MS. After disappearance of the starting carbonate, the reaction was stopped, the mixture cooled to room temperature, and the solvent evaporated.…”

Section: -(Dimethylamino)-2-(phenylsulfonyl)butyronitrile (14)mentioning

confidence: 99%

Sulfur and Nitrogen Mustard Carbonate Analogues

et al. 2012

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“…Residence time=0.225 mL/0.5 mL/min * 2 (two cycles)= 0.9 min During the N-alkylation of pyrrolidine with pentanol, we observed aromatized side-products at 250°C. Based on this unexpected result, we raised the temperature to 350°C to investigate if higher temperatures would lead to more dehydrogenated N-alkyl-pyrrole (23). In fact, we obtained directly the aromatized product in 84 % yield instead of N-alkyl-pyrrolidine.…”

mentioning

confidence: 99%

“…N-heterocyclization reactions of primary amines have also been achieved with glycols refluxing the reactants in toluene for 24 h in the presence of 0.1 eq. base [23]. The same group repeated the above reaction applying microwave (MW) heating, and significant acceleration was achieved (90 min) at 125°C [24].…”

mentioning

confidence: 99%

Important Industrial Procedures Revisited in Flow: Very Efficient Oxidation and N-Alkylation Reactions with High Atom-Economy

Sipos¹,

Gyóllai²,

Sipőcz³

et al. 2013

J Flow Chem

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The atom economy concept is one of the earliest recognition for green and sustainable aspects of organic synthesis. Over the years, novel technologies emerged that made this important feature of reactions into practice. Continuousflow devices increased the efficiency of the chemical transformations with novel process windows (high T, high p and heterogeneous packed catalysts etc.) and increased safety which turned the attention to reexamine old, industrial processes. Oxidation can be performed under flow catalytic conditions with molecular oxygen; alcohols can be oxidized to carbonyl compounds with high atom economy (AE=87 %). Using O 2 and 1 % Au/TiO 2 , alcohol oxidation in flow was achieved with complete conversion and >90 % yield. N-alkylation is another good example for achieving high atom economy. Under flow catalytic conditions (Raney Ni), amines were successfully reacted with alcohols directly (AE=91 %) with >90 % conversion and selectivity. In both examples, the effective residence time was less than 1 min. These two examples demonstrate the significant contribution of flow technology to the realization of key principles in green and sustainable chemistry.

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Ruthenium-Catalyzed N-Alkylation of Amines and Sulfonamides Using Borrowing Hydrogen Methodology

Cited by 615 publications

References 71 publications

A Survey of the Borrowing Hydrogen Approach to the Synthesis of some Pharmaceutically Relevant Intermediates

A Survey of the Borrowing Hydrogen Approach to the Synthesis of some Pharmaceutically Relevant Intermediates

Sulfur and Nitrogen Mustard Carbonate Analogues

Important Industrial Procedures Revisited in Flow: Very Efficient Oxidation and N-Alkylation Reactions with High Atom-Economy

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