PMID: 11929257Apr 4, 2002Paper

A general nickel-catalyzed hydroamination of 1,3-dienes by alkylamines: catalyst selection, scope, and mechanism

Journal of the American Chemical Society
Jan PawlasJohn F Hartwig

Abstract

A simple colorimetric assay of various transition-metal catalysts showed that the combination of DPPF, Ni(COD)(2), and acid is a highly active catalyst system for the hydroamination of dienes by alkylamines to form allylic amines. The scope of the reaction is broad; various primary and secondary alkylamines react with 1,3-dienes in the presence of these catalysts. Detailed mechanistic studies revealed the individual steps involved in the catalytic process. These studies uncovered unexpected thermodynamics for the addition of amines to pi-allyl nickel complexes: instead of the thermodynamics favoring the reaction of a nickel allyl with an amine to form an allylic amine, the thermodynamics favored reaction of a nickel(0) complex with allylic amine in the presence of acid to form a Ni(II) allyl. The realization of these thermodynamics led us to the discovery that nickel and some palladium complexes in the presence or absence of acid catalyze the exchange of the amino groups of allylic amines with free amines. This exchange process was used to reveal the relative thermodynamic stabilities of various allylic amines. In addition, this exchange reaction leads to racemization of allylic amines. Therefore, the relative rate for C-N bond...Continue Reading

References

Jul 18, 2001·Journal of the American Chemical Society·O LöberJ F Hartwig
Feb 19, 2002·Chemical Reviews·Mogens Johannsen, Karl Anker Jørgensen
Jun 18, 2001·Angewandte Chemie·Frauke Pohlki, Sven Doye

❮ Previous
Next ❯

Citations

Aug 31, 2007·Chemical Communications : Chem Comm·Cong LiuRoss A Widenhoefer
Oct 2, 2015·Chemical Reviews·Kunbing OuyangZhenfeng Xi
Apr 20, 2016·The Journal of Organic Chemistry·Ignacio ColomerAlma Viso
Jan 28, 2017·Journal of the American Chemical Society·Xiao-Hui Yang, Vy M Dong
Apr 26, 2017·Chemical Communications : Chem Comm·Jiangyan JingWanbin Zhang
Oct 14, 2014·Chemical Communications : Chem Comm·Meng-Guang ZhouShi-Kai Tian
Apr 20, 2014·Journal of the American Chemical Society·Matthew J GoldfogelSimon J Meek
Jan 15, 2015·Organic & Biomolecular Chemistry·Zehua YangWanbin Zhang
Feb 28, 2015·Chemical Reviews·Liangbin HuangLukas J Gooßen
Nov 9, 2017·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Sophie Bezzenine-LafolléeJérôme Hannedouche
Mar 25, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Violeta Rodriguez-RuizJérôme Hannedouche
Nov 29, 2011·Angewandte Chemie·Buddhadeb Chattopadhyay, Vladimir Gevorgyan
Oct 30, 2013·Angewandte Chemie·Justin M PiersonForrest E Michael
Jun 14, 2006·Angewandte Chemie·Berta Gómez-LorAntonio M Echavarren
Nov 7, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Isabelle AillaudEmmanuelle Schulz
Dec 7, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Elena Smolensky, Moris S Eisen
Jul 10, 2008·Angewandte Chemie·Sayak RoyWolfgang Kaim
Aug 13, 2005·Angewandte Chemie·Ludwig T KasparLutz Ackermann
Feb 3, 2006·Angewandte Chemie·Chad Brouwer, Chuan He
Jan 23, 2020·Angewandte Chemie·Daoyong ZhuJianrong Steve Zhou
Aug 14, 2013·Chemical Communications : Chem Comm·Man-Bo LiShi-Kai Tian
Mar 26, 2013·Chemistry : a European Journal·Xin QianCorinne Gosmini
Jun 4, 2020·Chemical Communications : Chem Comm·Ding-Wei JiQing-An Chen
Apr 8, 2020·Advanced Synthesis & Catalysis·Golo StorchScott J Miller
Jun 13, 2017·Angewandte Chemie·Alexander M HaydlMichael J Krische

❮ 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.