Arylruthenium(III) Porphyrin-Catalyzed C-H Oxidation and Epoxidation at Room Temperature and [RuV (Por)(O)(Ph)] Intermediate by Spectroscopic Analysis and Density Functional Theory Calculations

Journal of the American Chemical Society
Ka-Pan ShingChi-Ming Che

Abstract

The development of highly active and selective metal catalysts for efficient oxidation of hydrocarbons and identification of the reactive intermediates in the oxidation catalysis are long-standing challenges. In the rapid hydrocarbon oxidation catalyzed by ruthenium(IV) and -(III) porphyrins, the putative Ru(V)-oxo intermediates remain elusive. Herein we report that arylruthenium(III) porphyrins are highly active catalysts for hydrocarbon oxidation. Using catalyst [RuIII(TDCPP)(Ph)(OEt2)] (H2TDCPP = 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin), the oxidation of C-H bonds of various hydrocarbons with oxidant m-CPBA at room temperature gave alcohols/ketones in up to 99% yield within 1 h; use of [ nBu4N]IO4 as a mild alternative oxidant avoided formation of lactone from cyclic ketone in C-H oxidation, and the catalytic epoxidation with up to 99% yield and high selectivity (no aldehydes as side product) was accomplished within 5 min. UV-vis, electrospray ionization-mass spectrometry, resonance Raman, electron paramagnetic resonance, and kinetic measurements and density functional theory calculations lend evidence for the formation of Ru(V)-oxo intermediate [RuV(TDCPP)(O)(Ph)].

References

Apr 16, 2003·Accounts of Chemical Research·Stephen J Blanksby, G Barney Ellison
Aug 21, 2003·Journal of the American Chemical Society·Jasmine R Bryant, James M Mayer
May 21, 2005·The Journal of Organic Chemistry·Wing-Kei ChanChi-Ming Che
Jun 6, 2006·Inorganic Chemistry·Chuanqing WangJohn T Groves
Jul 1, 2006·Science·Rubén Mas-Ballesté, Lawrence Que
Mar 22, 2007·Journal of the American Chemical Society·David M HodgsonJean-Marc Paris
Feb 6, 2009·Journal of the American Chemical Society·Zhengzheng PanMartin Newcomb
Jun 26, 2009·Journal of the American Chemical Society·Seth R Bell, John T Groves
Jul 2, 2009·Chemical Communications : Chem Comm·Chi-Ming Che, Jie-Sheng Huang
Oct 13, 2009·Accounts of Chemical Research·Javier J ConcepcionThomas J Meyer
Jan 18, 2011·Chemical Society Reviews·Meng Zhou, Robert H Crabtree
Feb 18, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Chun-Guang LiuZhong-Min Su
Jun 28, 2011·Journal of the American Chemical Society·Masato MurakamiShunichi Fukuzumi
Feb 22, 2012·Science·M Christina White
Jun 22, 2012·Nature Chemistry·Markus G ScheibelSven Schneider
Feb 19, 2013·Proceedings of the National Academy of Sciences of the United States of America·Dooshaye MoonshiramYulia Pushkar
Nov 20, 2013·Chemical Reviews·Miao SunJean-Marie Basset
Apr 29, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Rui ZhangMartin Newcomb
Feb 17, 2017·Chemical Reviews·Vincent C-C WangSunney I Chan
Nov 8, 2017·Chemical Reviews·Joseph T GrantIve Hermans

❮ Previous
Next ❯

Citations

Mar 7, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Alejandro Torregrosa-Chinillach, Rafael Chinchilla
Jul 29, 2021·Journal of the American Chemical Society·Jaruwan AmtawongT Don Tilley
Mar 12, 2019·The Journal of Organic Chemistry·Xianying GaoYangjie Wu
Jan 17, 2020·The Journal of Organic Chemistry·Peihe LiJinghai Liu
Jan 25, 2019·Journal of Agricultural and Food Chemistry·Raheleh RavanfarAlireza Abbaspourrad
Sep 30, 2020·The Journal of Organic Chemistry·Tomoya IshizukaTakahiko Kojima

❮ 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.