Selective room-temperature hydrogenation of amides to amines and alcohols catalyzed by a ruthenium pincer complex and mechanistic insight

Sayan Kar; Michael Rauch; Amit Kumar; Gregory Leitus; Yehoshoa Ben-David; David Milstein

doi:10.1021/acscatal.0c01406

Selective room-temperature hydrogenation of amides to amines and alcohols catalyzed by a ruthenium pincer complex and mechanistic insight

Sayan Kar, Michael Rauch, Amit Kumar, Gregory Leitus, Yehoshoa Ben-David, David Milstein

School of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

We report a room-temperature protocol for the hydrogenation of various amides to produce amines and alcohols. Compared with most previous reports for this transformation, which use high temperatures (typically, 100–200 °C) and H₂ pressures (10–100 bar), this system proceeds under extremely mild conditions (RT, 5–10 bar of H₂). The hydrogenation is catalyzed by well-defined ruthenium-PNNH pincer complexes (0.5 mol %) with potential dual modes of metal–ligand cooperation. An unusual Ru-amidate complex was formed and crystallographically characterized. Mechanistic investigations indicate that the room-temperature hydrogenation proceeds predominantly via the Ru–N amido/amine metal–ligand cooperation.

Original language	English
Pages (from-to)	5511-5515
Number of pages	5
Journal	ACS Catalysis
Volume	10
Issue number	10
Early online date	21 Apr 2020
DOIs	https://doi.org/10.1021/acscatal.0c01406
Publication status	Published - 15 May 2020

Keywords

Amide
Hydrogenation
Metal-ligand cooperation
Ruthenium-pincer
Room-tempature
Ruthenium amidate complex

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10.1021/acscatal.0c01406Licence: CC BY

Kar_2020_ACSC_Hydrogenation_CC
Copyright © 2020 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
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Cite this

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title = "Selective room-temperature hydrogenation of amides to amines and alcohols catalyzed by a ruthenium pincer complex and mechanistic insight",

abstract = "We report a room-temperature protocol for the hydrogenation of various amides to produce amines and alcohols. Compared with most previous reports for this transformation, which use high temperatures (typically, 100–200 °C) and H2 pressures (10–100 bar), this system proceeds under extremely mild conditions (RT, 5–10 bar of H2). The hydrogenation is catalyzed by well-defined ruthenium-PNNH pincer complexes (0.5 mol %) with potential dual modes of metal–ligand cooperation. An unusual Ru-amidate complex was formed and crystallographically characterized. Mechanistic investigations indicate that the room-temperature hydrogenation proceeds predominantly via the Ru–N amido/amine metal–ligand cooperation.",

keywords = "Amide, Hydrogenation, Metal-ligand cooperation, Ruthenium-pincer, Room-tempature, Ruthenium amidate complex",

author = "Sayan Kar and Michael Rauch and Amit Kumar and Gregory Leitus and Yehoshoa Ben-David and David Milstein",

note = "This research was supported by the European Research Council (ERC AdG 692775). D.M. holds the Israel Matz Professorial Chair of Organic Chemistry. S.K. acknowledges the Sustainability and Energy Research Initiative (SAERI) of the Weizmann Institute of Science for a research fellowship. M.R. acknowledges the Zuckerman STEM Leadership Program for a research fellowship.",

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doi = "10.1021/acscatal.0c01406",

language = "English",

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T1 - Selective room-temperature hydrogenation of amides to amines and alcohols catalyzed by a ruthenium pincer complex and mechanistic insight

AU - Kar, Sayan

AU - Rauch, Michael

AU - Kumar, Amit

AU - Leitus, Gregory

AU - Ben-David, Yehoshoa

AU - Milstein, David

N1 - This research was supported by the European Research Council (ERC AdG 692775). D.M. holds the Israel Matz Professorial Chair of Organic Chemistry. S.K. acknowledges the Sustainability and Energy Research Initiative (SAERI) of the Weizmann Institute of Science for a research fellowship. M.R. acknowledges the Zuckerman STEM Leadership Program for a research fellowship.

PY - 2020/5/15

Y1 - 2020/5/15

N2 - We report a room-temperature protocol for the hydrogenation of various amides to produce amines and alcohols. Compared with most previous reports for this transformation, which use high temperatures (typically, 100–200 °C) and H2 pressures (10–100 bar), this system proceeds under extremely mild conditions (RT, 5–10 bar of H2). The hydrogenation is catalyzed by well-defined ruthenium-PNNH pincer complexes (0.5 mol %) with potential dual modes of metal–ligand cooperation. An unusual Ru-amidate complex was formed and crystallographically characterized. Mechanistic investigations indicate that the room-temperature hydrogenation proceeds predominantly via the Ru–N amido/amine metal–ligand cooperation.

AB - We report a room-temperature protocol for the hydrogenation of various amides to produce amines and alcohols. Compared with most previous reports for this transformation, which use high temperatures (typically, 100–200 °C) and H2 pressures (10–100 bar), this system proceeds under extremely mild conditions (RT, 5–10 bar of H2). The hydrogenation is catalyzed by well-defined ruthenium-PNNH pincer complexes (0.5 mol %) with potential dual modes of metal–ligand cooperation. An unusual Ru-amidate complex was formed and crystallographically characterized. Mechanistic investigations indicate that the room-temperature hydrogenation proceeds predominantly via the Ru–N amido/amine metal–ligand cooperation.

KW - Amide

KW - Hydrogenation

KW - Metal-ligand cooperation

KW - Ruthenium-pincer

KW - Room-tempature

KW - Ruthenium amidate complex

U2 - 10.1021/acscatal.0c01406

DO - 10.1021/acscatal.0c01406

M3 - Article

SN - 2155-5435

VL - 10

SP - 5511

EP - 5515

JO - ACS Catalysis

JF - ACS Catalysis

IS - 10

ER -

Selective room-temperature hydrogenation of amides to amines and alcohols catalyzed by a ruthenium pincer complex and mechanistic insight

Abstract

Keywords

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