Reduction and Reductive Deuteration of Tertiary Amides Mediated by Sodium Dispersions with Distinct Proton Donor-Dependent Chemoselectivity

The Journal of Organic Chemistry
Bin ZhangJie An

Abstract

A practical and scalable single electron transfer reduction mediated by sodium dispersions has been developed for the reduction and reductive deuteration of tertiary amides. The chemoselectivity of this method highly depends on the nature of the proton donor. The challenging reduction via C-N bond cleavage has been achieved using Na/EtOH, affording alcohol products, while the use of Na/NaOH/H2O leads to the formation of amines via selective C-O scission. Sodium dispersions with high specific surface areas are crucial to obtain high yields and good chemoselectivity. This new method tolerates a range of tertiary amides. Moreover, the corresponding reductive deuterations mediated by Na/EtOD- d1 and Na/NaOH/D2O afford useful α,α-dideuterio alcohols and α,α-dideuterio amines with an excellent deuterium content.

References

Jun 10, 2006·Organic & Biomolecular Chemistry·John S CareyMike T Williams
Jul 14, 2006·Chemical Reviews·Elizabeth R Burkhardt, Karl Matos
Feb 5, 2009·Journal of the American Chemical Society·M Haniti S A HamidJonathan M J Williams
Mar 9, 2011·Journal of the American Chemical Society·Masato ItoTakao Ikariya
Jun 8, 2011·Angewandte Chemie·Daniele AddisMatthias Beller
Jun 28, 2011·Organic Letters·Zeyneb SahliChristian Bruneau
Aug 23, 2011·Chemical Communications : Chem Comm·Michal SzostakDavid J Procter
Feb 7, 2012·Chemical Communications : Chem Comm·Shoubhik DasMatthias Beller
Jun 19, 2012·Journal of the American Chemical Society·Lorenz NeubertMatthias Beller
Jul 10, 2012·Journal of the American Chemical Society·Chen Cheng, Maurice Brookhart
Jan 30, 2013·Chemical Communications : Chem Comm·Mario JanjetovicGöran Hilmersson
Jan 28, 2014·Journal of the American Chemical Society·Michal SzostakDavid J Procter
Oct 14, 2014·Chemical Communications : Chem Comm·Alexey VolkovHans Adolfsson
Dec 3, 2014·Chemical Communications : Chem Comm·Pei-Qiang HuangJian-Feng Zheng
Jan 15, 2015·Organic Letters·Oleksandr O KovalenkoHans Adolfsson
Apr 22, 2016·The Journal of Organic Chemistry·Pei-Qiang HuangYan-Rong Wang
Sep 22, 2016·Angewandte Chemie·Debabrata MukherjeeJun Okuda
Oct 25, 2016·Chemical Society Reviews·Alexey VolkovHans Adolfsson
Jan 31, 2017·Journal of the American Chemical Society·Loorthuraja RasuSteven H Bergens
Nov 11, 2017·Science·Yong Yao LohDavid W C MacMillan
Nov 22, 2017·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Shicheng Shi, Michal Szostak

❮ Previous
Next ❯

Citations

Feb 15, 2019·Angewandte Chemie·Derek Yiren OngShunsuke Chiba
Jan 21, 2020·Chemistry, an Asian Journal·Subramanian ThiyagarajanChidambaram Gunanathan
May 20, 2020·Science Advances·Minyan WangZhuangzhi Shi
Jan 31, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Hengzhao LiJie An
Aug 24, 2019·Organic Letters·Ming-Hui ZhuWen-Bo Liu
Nov 7, 2019·The Journal of Organic Chemistry·Yuxuan DingJie An
Oct 15, 2019·The Journal of Organic Chemistry·Yuxuan DingJie An
May 31, 2018·Organic Letters·Peng LeiJie An

❮ Previous
Next ❯

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.