Mechanistic insight into borrowing-hydrogen<i>N</i>-alkylation catalyzed by an MLC catalyst with dual proton-responsive sites

Mei, Lan; Du, Min; Zhang, Yuan; Hou, Cheng

doi:10.1039/d2dt02597c

Cited by 4 publications

(1 citation statement)

References 49 publications

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“…This overall mechanistic picture is in line with previous DFT studies reported on hydrogen borrowing processes for the N-alkylation of amines by alcohols catalysed by manganese, 36 cobalt, 37 nickel, 38 ruthenium, [39][40][41] and iridium. 42,43 Figure 3 A) Stochiometric reactivity between activated complex (2) with ethanolamine; B) simplified catalytic mechanism of (de)hydrogenation; C) Energies (G423.15K) of alcohol dehydrogenation for monomer, dimer and trimer (PBE0-D3(BJ)PCM(THF)/def2-TZVP//RI-BP86PCM(THF)/def2-SVP).…”

Section: Mechanistic Investigationssupporting

confidence: 91%

Direct Synthesis of Partially Ethoxylated Branched Polyethylenimine from Ethanolamine

Brodie,

Goodfellow,

Owen

et al. 2023

Preprint

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We report here a new method to make a branched and partially ethoxylated polyethyleneimine derivative directly from ethanolamine. The polymerization reaction is catalysed by a pincer complex of Earth-abundant metal, manganese, and produces water as the only byproduct. Industrial processes to produce polyethyleneimines involve the transformation of ethanolamine to a highly toxic chemical, aziridine, by an energy-intensive/waste-generating process followed by the ring-opening polymerization of aziridine. Through bypassing the need to produce a highly toxic feedstock, the reported method herein is greener than the current state-of-the-art. We propose that the polymerization process follows a hydrogen borrowing pathway that involves (a) dehydrogenation of ethanolamine to form 2-aminoacetaldehyde, (b) dehydrative coupling of 2-aminoacetaldehyde with ethanolamine to form an imine derivative, and (c) subsequent hydrogenation of imine derivative to form alkylated amines.

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Section: Mechanistic Investigationssupporting

confidence: 91%

Direct Synthesis of Partially Ethoxylated Branched Polyethylenimine from Ethanolamine

Brodie,

Goodfellow,

Owen

et al. 2023

Preprint

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New synthetic method for ring-fused quinazoline by palladium-catalyzed oxidative cyclization of 2-aminobenzyl alcohol: Chiral separation and structural analysis

Enda,

Nakayama,

Suzuki

et al. 2024

Journal of Molecular Structure

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Direct synthesis of partially ethoxylated branched polyethylenimine from ethanolamine

Brodie,

Goodfellow,

Andrews

et al. 2024

Nat Commun

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We report here a method to make a branched and partially ethoxylated polyethyleneimine derivative directly from ethanolamine. The polymerization reaction is catalysed by a pincer complex of Earth-abundant metal, manganese, and produces water as the only byproduct. Industrial processes to produce polyethyleneimines involve the transformation of ethanolamine to a highly toxic chemical, aziridine, by an energy-intensive/waste-generating process followed by the ring-opening polymerization of aziridine. The reported method bypasses the need to produce a highly toxic intermediate and presents advantages over the current state-of-the-art. We propose that the polymerization process follows a hydrogen borrowing pathway that involves (a) dehydrogenation of ethanolamine to form 2-aminoacetaldehyde, (b) dehydrative coupling of 2-aminoacetaldehyde with ethanolamine to form an imine derivative, and (c) subsequent hydrogenation of imine derivative to form alkylated amines.

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Mechanistic insight into borrowing-hydrogenN-alkylation catalyzed by an MLC catalyst with dual proton-responsive sites

Abstract: Metal-ligand cooperation (MLC) catalysis is one of the most important concepts in the field of organometallic catalysis. However, the diverse functional ligands result in ambiguous mechanisms and constrain the understanding...

Cited by 4 publications

References 49 publications

Direct Synthesis of Partially Ethoxylated Branched Polyethylenimine from Ethanolamine

Direct Synthesis of Partially Ethoxylated Branched Polyethylenimine from Ethanolamine

New synthetic method for ring-fused quinazoline by palladium-catalyzed oxidative cyclization of 2-aminobenzyl alcohol: Chiral separation and structural analysis

Direct synthesis of partially ethoxylated branched polyethylenimine from ethanolamine

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