Phase-Transfer Activation of Transition Metal Catalysts

Chemistry : a European Journal
Robert TubaJohn A Gladysz

Abstract

With metal-based catalysts, it is quite common that a ligand (L) must first dissociate from a catalyst precursor (L'n M-L) to activate the catalyst. The resulting coordinatively unsaturated active species (L'n M) can either back react with the ligand in a k-1 step, or combine with the substrate in a k2 step. When dissociation is not rate determining and k-1 [L] is greater than or comparable to k2 [substrate], this slows the rate of reaction. By introducing a phase label onto the ligand L and providing a suitable orthogonal liquid or solid phase, dramatic rate accelerations can be achieved. This phenomenon is termed "phase-transfer activation". In this Concept, some historical antecedents are reviewed, followed by successful applications involving fluorous/organic and aqueous/organic liquid/liquid biphasic catalysis, and liquid/solid biphasic catalysis. Variants that include a chemical trap for the phase-labeled ligands are also described.

References

Jul 6, 2001·Journal of the American Chemical Society·M S SanfordR H Grubbs
Oct 10, 2002·Chemical Reviews·Jun-Ichi Yoshida, Kenichiro Itami
Oct 31, 2002·Journal of the American Chemical Society·Mounir El BakkariJean-Marc Vincent
Jan 23, 2003·Chemical Communications : Chem Comm·Roy A PerianaGaurav Bhalla
Aug 14, 2003·Journal of the American Chemical Society·Jennifer A LoveRobert H Grubbs
Aug 19, 2003·Angewandte Chemie·Yinghuai ZhuM Frederick Hawthorne
Oct 2, 2003·Chemical Communications : Chem Comm·Eric F ConnorRobert H Grubbs
Jan 8, 2004·Journal of the American Chemical Society·Jonas OxgaardRoy A Periana
Jun 17, 2004·Journal of the American Chemical Society·Soon Hyeok HongRobert H Grubbs
Mar 25, 2005·Organic Letters·Andrew StreitwieserNicole R Davis
Mar 16, 2006·Journal of the American Chemical Society·Soon Hyeok Hong, Robert H Grubbs
Jun 17, 2006·Chemical Communications : Chem Comm·Rosenildo Corrêa da Costa, J A Gladysz
Jun 6, 2007·Journal of the American Chemical Society·Soon Hyeok HongRobert H Grubbs
Jul 31, 2007·Organic Letters·Chayanant HongfaDavid E Bergbreiter
Dec 25, 2007·Organic Letters·Crestina S ConsortiJaïrton Dupont
Nov 5, 2008·Angewandte Chemie·Daniel Burtscher, Karol Grela
Jan 15, 2009·Organic Letters·Chayanant HongfaDavid E Bergbreiter
Dec 17, 2009·Chemical Reviews·Georgios C Vougioukalakis, Robert H Grubbs
Jan 13, 2010·The Journal of Organic Chemistry·David E Bergbreiter, Yun-Chin Yang
May 8, 2010·Chemical Society Reviews·Stijn MonsaertFrancis Verpoort
Jan 22, 2011·Chemical Communications : Chem Comm·Michaela ZirngastChristian Slugovc
Oct 25, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Yuval VidavskyN Gabriel Lemcoff
Jan 28, 2012·Organometallics·Renee M ThomasRobert H Grubbs
Feb 13, 2014·Macromolecular Rapid Communications·Stefan Naumann, Michael R Buchmeiser
May 23, 2015·The Journal of the Acoustical Society of America·Sriram Boothalingam, David W Purcell
Aug 25, 2015·Journal of the American Chemical Society·Zhenxing XiJohn A Gladysz

❮ Previous
Next ❯

Citations

Oct 13, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Bertrand BraibantDaniel Meyer

❮ 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.