Efficient alkylation of ketones with primary alcohols catalyzed by ruthenium(II)/P,N ligand complexes

Shi Yuan Liu; Lin Yan Xu; Chun Yu Liu; Zhi Gang Ren; David James Young; Jian Ping Lang

doi:10.1016/j.tet.2017.03.022

Efficient alkylation of ketones with primary alcohols catalyzed by ruthenium(II)/P,N ligand complexes

Shi Yuan Liu, Lin Yan Xu, Chun Yu Liu, Zhi Gang Ren, David James Young, Jian Ping Lang

Research output: Contribution to journal › Article

Abstract

An efficient catalytic system containing [RuCl₂(η⁶-p-cymene)]₂ and one P,N ligand, N-diphenylphosphino-2-aminopyridine (L1) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by ¹H NMR and ESI-MS reveals a stable cationic L1-coordinated ruthenium hydride intermediate, identified as [Ru(η⁶-p-cymene)(κ²-L1)H]⁺. Organic intermediates consistent with a three-step dehydrogenation, alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.

Original language	English
Pages (from-to)	2374-2381
Number of pages	8
Journal	Tetrahedron
Volume	73
Issue number	17
DOIs	https://doi.org/10.1016/j.tet.2017.03.022
Publication status	Published - 27 Apr 2017
Externally published	Yes

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@article{ef0444cc77fc44a9bd77c3ad4e1e24bd,

title = "Efficient alkylation of ketones with primary alcohols catalyzed by ruthenium(II)/P,N ligand complexes",

abstract = "An efficient catalytic system containing [RuCl2(η6-p-cymene)]2 and one P,N ligand, N-diphenylphosphino-2-aminopyridine (L1) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by 1H NMR and ESI-MS reveals a stable cationic L1-coordinated ruthenium hydride intermediate, identified as [Ru(η6-p-cymene)(κ2-L1)H]+. Organic intermediates consistent with a three-step dehydrogenation, alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.",

keywords = "Alcohol, Alkylation, P,N hybrid ligand, Ruthenium hydride, Ruthenium(II)",

author = "Liu, {Shi Yuan} and Xu, {Lin Yan} and Liu, {Chun Yu} and Ren, {Zhi Gang} and Young, {David James} and Lang, {Jian Ping}",

year = "2017",

month = apr,

day = "27",

doi = "10.1016/j.tet.2017.03.022",

language = "English",

volume = "73",

pages = "2374--2381",

journal = "Tetrahedron: the international journal for the rapid publication of full original research papers and critical reviews in organic chemistr",

issn = "0040-4020",

publisher = "Elsevier",

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TY - JOUR

T1 - Efficient alkylation of ketones with primary alcohols catalyzed by ruthenium(II)/P,N ligand complexes

AU - Liu, Shi Yuan

AU - Xu, Lin Yan

AU - Liu, Chun Yu

AU - Ren, Zhi Gang

AU - Young, David James

AU - Lang, Jian Ping

PY - 2017/4/27

Y1 - 2017/4/27

N2 - An efficient catalytic system containing [RuCl2(η6-p-cymene)]2 and one P,N ligand, N-diphenylphosphino-2-aminopyridine (L1) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by 1H NMR and ESI-MS reveals a stable cationic L1-coordinated ruthenium hydride intermediate, identified as [Ru(η6-p-cymene)(κ2-L1)H]+. Organic intermediates consistent with a three-step dehydrogenation, alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.

AB - An efficient catalytic system containing [RuCl2(η6-p-cymene)]2 and one P,N ligand, N-diphenylphosphino-2-aminopyridine (L1) was loaded in catalyzing the alkylation of ketones with primary alcohols for a diverse array of substrates. Other five P,N ligands based on pyridin-2-amine and pyrimidin-2-amine were also examined in this reaction to explore the influence of steric hindrance and electronic effects. Monitoring by 1H NMR and ESI-MS reveals a stable cationic L1-coordinated ruthenium hydride intermediate, identified as [Ru(η6-p-cymene)(κ2-L1)H]+. Organic intermediates consistent with a three-step dehydrogenation, alkylation and hydrogenation pathway were also observed. The final step in this reaction, the ruthenium-catalysed transfer hydrogenation reduction of α,β-unsaturated ketone with benzyl alcohol was performed separately.

KW - Alcohol

KW - Alkylation

KW - P,N hybrid ligand

KW - Ruthenium hydride

KW - Ruthenium(II)

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DO - 10.1016/j.tet.2017.03.022

M3 - Article

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VL - 73

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EP - 2381

JO - Tetrahedron: the international journal for the rapid publication of full original research papers and critical reviews in organic chemistr

JF - Tetrahedron: the international journal for the rapid publication of full original research papers and critical reviews in organic chemistr

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