DFT studies on mechanistic origins of ligand-controlled selectivity in Pd-catalyzed non-decarbonylative and decarbonylative reductive conversion of acyl fluoride

Dalton Transactions : an International Journal of Inorganic Chemistry
Hujun XieWenjun Fang

Abstract

The mechanisms and origins for ligand-controlled non-decarbonylative and decarbonylative conversions of acyl fluorides catalyzed by palladium catalysts with different ligands tricyclohexylphosphine (PCy3) and 1,2-bis(dicyclohexylphosphino)ethane (DCPE) have been investigated by density functional theory (DFT) calculations. In the case of the DCPE ligand, the favorable catalytic cycle contains four steps, oxidative addition, decarbonylation, transmetallation and reductive elimination. In the case of the PCy3 ligand, the favorable catalytic cycle proceeds by three steps, oxidative addition, transmetallation and reductive elimination. Distortion/interaction analysis indicated that decarbonylation does not occur for PCy3 owing to the repulsive interaction between PCy3 and substrates. Present calculations agree with the experimental observations and understanding these surprising ligand-controlled non-decarbonylative and decarbonylative selectivity reactions could provide important insights into the development of selective catalyst systems.

References

Apr 1, 2003·Journal of Computational Chemistry·Maurizio CossiVincenzo Barone
May 8, 2003·Journal of the American Chemical Society·Jae-Young Lee, Gregory C Fu
Apr 21, 2006·Organic Letters·Kyoungsoo Lee, Robert E Maleczka
Aug 10, 2007·Journal of the American Chemical Society·Daniel H Ess, K N Houk
Oct 5, 2007·Journal of the American Chemical Society·Claude Y LegaultK N Houk
Mar 22, 2008·Angewandte Chemie·Lukas J GoossenKäthe Goossen
Jul 11, 2008·Journal of the American Chemical Society·Daniel H Ess, K N Houk
Jan 25, 2013·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Marco BlangettiPaolo Venturello
Apr 5, 2014·Chemical Society Reviews·Israel Fernández, F Matthias Bickelhaupt
Jun 20, 2017·ACS Catalysis·Jacob E Dander, Neil K Garg
Jul 8, 2017·Chemical Society Reviews·Ryosuke TakiseJunichiro Yamaguchi
Feb 27, 2018·Angewandte Chemie·Sinead T Keaveney, Franziska Schoenebeck

❮ Previous
Next ❯

Citations

Apr 15, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Liyan FuYasushi Nishihara
Mar 7, 2020·Organic Letters·Liyan FuYasushi Nishihara

❮ Previous
Next ❯

Methods Mentioned

BETA
acylation

Software Mentioned

Gaussian09
M06

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.