Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: integrating nucleophilicity with Lewis acidic activation.

Chemical Science
Mrinal BhuniaSwadhin K Mandal

Abstract

An abnormal N-heterocyclic carbene (aNHC) based potassium complex was used as a transition metal-free catalyst for reduction of primary amides to corresponding primary amines under ambient conditions. Only 2 mol% loading of the catalyst exhibits a broad substrate scope including aromatic, aliphatic and heterocyclic primary amides with excellent functional group tolerance. This method was applicable for reduction of chiral amides and utilized for the synthesis of pharmaceutically valuable precursors on a gram scale. During mechanistic investigation, several intermediates were isolated and characterized through spectroscopic techniques and one of the catalytic intermediates was characterized through single-crystal XRD. A well-defined catalyst and isolable intermediate along with several stoichiometric experiments, in situ NMR experiments and the DFT study helped us to sketch the mechanistic pathway for this reduction process unravelling the dual role of the catalyst involving nucleophilic activation by aNHC along with Lewis acidic activation by K ions.

References

Feb 19, 2002·Chemical Reviews·Mogens Johannsen, Karl Anker Jørgensen
Aug 14, 2003·Chemical Reviews·Barry M Trost, Matthew L Crawley
Jul 27, 2007·Chemical Communications : Chem Comm·Angel A Núñez MagroDavid J Cole-Hamilton
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Sep 26, 2008·Chemistry : a European Journal·Stephan EnthalerMatthias Beller
Oct 11, 2008·Angewandte Chemie·Chidambaram Gunanathan, David Milstein
Nov 12, 2009·Angewandte Chemie·Yusuke SunadaHideo Nagashima
Jan 29, 2010·Journal of the American Chemical Society·Shoubhik DasMatthias Beller
Jul 31, 2010·Angewandte Chemie·Dennis PingenDieter Vogt
Sep 22, 2010·Angewandte Chemie·Jessica L Klinkenberg, John F Hartwig
Sep 23, 2010·Angewandte Chemie·Dmitry V Gutsulyak, Georgii I Nikonov
Apr 27, 2011·Inorganic Chemistry·Michael S HillDugald J MacDougall
Nov 20, 2012·Angewandte Chemie·Jayanta ChatterjeeHorst Kessler
Aug 21, 2015·Chemical Reviews·Alessandro GandiniEliane Trovatti
Nov 3, 2015·Chemical Reviews·Irina DelidovichRegina Palkovits
Sep 22, 2016·Angewandte Chemie·Debabrata MukherjeeJun Okuda
Nov 20, 2016·Angewandte Chemie·Samaresh Chandra SauSwadhin K Mandal
Jun 24, 2017·Journal of the American Chemical Society·Mathew D AnkerLaurent Maron
Sep 25, 2017·Science·Rajenahally V JagadeeshMatthias Beller
Jan 1, 2016·Chemical Science·Catherine WeetmanMary F Mahon
Oct 10, 2018·Nature Communications·Thirusangumurugan SenthamaraiRajenahally V Jagadeesh
Mar 8, 2019·Chemical Science·Samaresh Chandra SauSwadhin K Mandal
Apr 24, 2019·Nature Chemistry·Alessandro RuffoniDaniele Leonori
Apr 24, 2019·The Journal of Organic Chemistry·Wubing YaoZheng Huang
Sep 19, 2019·Chemical Communications : Chem Comm·Hari S DasSwadhin K Mandal

❮ Previous
Next ❯

Citations

May 23, 2021·Chemistry : a European Journal·P SreejyothiSwadhin K Mandal
Feb 12, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Milan Kumar BisaiSakya S Sen
Apr 25, 2021·Angewandte Chemie·Pradip Ghosh, Axel Jacobi von Wangelin
Sep 28, 2021·Chemical Communications : Chem Comm·Rohit KumarSakya S Sen
Nov 18, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Andrey Y Khalimon

❮ Previous
Next ❯

Methods Mentioned

BETA
NMR
X-ray

Software Mentioned

Gaussian
Superflip
ShelXL
Seed
Olex2

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

© 2021 Meta ULC. All rights reserved