Palladium-catalyzed aerobic intermolecular cyclization of acrylic acid with 1-octene to afford α-methylene-γ-butyrolactones: the remarkable effect of continuous water removal from the reaction mixture and analysis of the reaction by kinetic, ESI-MS, and XAFS measurements

Chemistry : a European Journal
Yasuyuki MiyoshiKoji Yonehara

Abstract

Further study of our aerobic intermolecular cyclization of acrylic acid with 1-octene to afford α-methylene-γ-butyrolactones, catalyzed by the Pd(OCOCF(3))(2)/Cu(OAc)(2)⋅H(2)O system, has clarified that the accumulation of water generated from oxygen during the reaction causes deactivation of the Cu cocatalyst. This prevents regeneration of the active Pd catalyst and, thus, has a harmful influence on the progress of the cyclization. As a result, both the substrate conversion and product yield are efficiently improved by continuous removal of water from the reaction mixture. Detailed analysis of the kinetic and spectroscopic measurements performed under the condition of continuous water removal demonstrates that the cyclization proceeds in four steps: 1) equilibrium coordination of 1-octene to the Pd acrylate species, 2) Markovnikov-type acryloxy palladation of 1-octene (1,2-addition), 3) intramolecular carbopalladation, and 4) β-hydride elimination. Byproduct 2-acryloxy-1-octene is formed by β-hydride elimination after step 2). These cyclization steps fit the Michaelis-Menten equation well and β-hydride elimination is considered to be a rate-limiting step in the formation of the products. Spectroscopic data agree sufficiently w...Continue Reading

References

Oct 25, 2001·The Journal of Organic Chemistry·Takahiro NishimuraSakae Uemura
Sep 18, 2002·Accounts of Chemical Research·Roger A SheldonArné Dijksman
Dec 12, 2002·Journal of the American Chemical Society·Moniek TrompDiek C Koningsberger
Dec 3, 2003·Chemical Communications : Chem Comm·Steven G FiddyRichard Oldman
Aug 19, 2004·Journal of the American Chemical Society·Michael M KonnickShannon S Stahl
Sep 8, 2004·Organic & Biomolecular Chemistry·Matthew S Sigman, Mitchell J Schultz
Jan 13, 2005·Journal of the American Chemical Society·Moniek TrompDavid E Ramaker
Mar 10, 2005·Journal of the American Chemical Society·Yongsheng ChenTom Autrey
Jun 9, 2005·Journal of the American Chemical Society·Mitchell J SchultzMatthew S Sigman
Sep 22, 2005·Journal of the American Chemical Society·Jason M KeithWilliam A Goddard
Oct 20, 2005·Journal of the American Chemical Society·Jaime A MuellerMatthew S Sigman
Dec 15, 2005·Journal of the American Chemical Society·Raissa M TrendBrian M Stoltz
Dec 15, 2005·Journal of the American Chemical Society·Vitaliy I Timokhin, Shannon S Stahl
Feb 24, 2006·Journal of the American Chemical Society·Melanie C DenneyKaren I Goldberg
Feb 25, 2006·The Journal of Organic Chemistry·Bradley A SteinhoffShannon S Stahl
Mar 30, 2006·Journal of the American Chemical Society·Bradley A Steinhoff, Shannon S Stahl
Jul 27, 2006·Journal of the American Chemical Society·Robert J Nielsen, William A Goddard
Sep 21, 2006·Angewandte Chemie·Keith M Gligorich, Matthew S Sigman
Mar 14, 2007·Inorganic Chemistry·Candace N Cornell, Matthew S Sigman
Mar 21, 2007·Journal of the American Chemical Society·Brian V Popp, Shannon S Stahl
Apr 19, 2007·Journal of the American Chemical Society·Guosheng Liu, Shannon S Stahl
Aug 7, 2007·Journal of the American Chemical Society·Jason M KeithJonas Oxgaard
Sep 21, 2007·Journal of the American Chemical Society·John A KeithWilliam A Goddard
Nov 2, 2007·Chemical Reviews·Egle M BeccalliSilvia Sottocornola
Mar 22, 2008·Angewandte Chemie·Lukas J GoossenKäthe Goossen
Sep 10, 2008·Journal of the American Chemical Society·Song LinZhang-Jie Shi
Jan 13, 2009·Journal of the American Chemical Society·Jason M Keith, William A Goddard

❮ 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.