Mechanistic Guidance Leads to Enhanced Site-Selectivity in C–H Oxidation Reactions Catalyzed by Ruthenium bis(Bipyridine) Complexes

ACS Catalysis ◽  
2021 ◽  
pp. 10479-10486
Author(s):  
Jeremy D. Griffin ◽  
David B. Vogt ◽  
J. Du Bois ◽  
Matthew S. Sigman
Keyword(s):  
Oxidation Reactions ◽  
Site Selectivity

scholarly journals Unconventional mechanism and selectivity of the Pd-catalyzed C–H bond lactonization in aromatic carboxylic acid

2022 ◽  
Vol 13 (1) ◽  
Author(s):  
Li-Ping Xu ◽  
Shaoqun Qian ◽  
Zhe Zhuang ◽  
Jin-Quan Yu ◽  
Djamaladdin G. Musaev
Keyword(s):  
Controlling Factors ◽  
Environmentally Benign ◽  
Oxidation Reactions ◽  
Aromatic Carboxylic Acid ◽  
Research Mission ◽  
Site Selectivity ◽  
Substitution Mechanism ◽  
Rate Limiting ◽  
Base Substrate ◽  
Formation Step

AbstractThe search for more effective and highly selective C–H bond oxidation of accessible hydrocarbons and biomolecules is a greatly attractive research mission. The elucidating of mechanism and controlling factors will, undoubtedly, help to broaden scope of these synthetic protocols, and enable discovery of more efficient, environmentally benign, and highly practical new C–H oxidation reactions. Here, we reveal the stepwise intramolecular SN2 nucleophilic substitution mechanism with the rate-limiting C–O bond formation step for the Pd(II)-catalyzed C(sp3)–H lactonization in aromatic 2,6-dimethylbenzoic acid. We show that for this reaction, the direct C–O reductive elimination from both Pd(II) and Pd(IV) (oxidized by O2 oxidant) intermediates is unfavorable. Critical factors controlling the outcome of this reaction are the presence of the η3-(π-benzylic)–Pd and K+–O(carboxylic) interactions. The controlling factors of the benzylic vs ortho site-selectivity of this reaction are the: (a) difference in the strains of the generated lactone rings; (b) difference in the strengths of the η3-(π-benzylic)–Pd and η2-(π-phenyl)–Pd interactions, and (c) more pronounced electrostatic interaction between the nucleophilic oxygen and K+ cation in the ortho-C–H activation transition state. The presented data indicate the utmost importance of base, substrate, and ligand in the selective C(sp3)–H bond lactonization in the presence of C(sp2)–H.

Chelation-assisted transition metal-catalysed C–H chalcogenylations

2020 ◽  
Vol 7 (8) ◽  
pp. 1022-1060 ◽  
Author(s):  
Wenbo Ma ◽  
Nikolaos Kaplaneris ◽  
Xinyue Fang ◽  
Linghui Gu ◽  
Ruhuai Mei ◽  
...  
Keyword(s):  
Transition Metal ◽  
Recent Advances ◽  
Site Selectivity ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

This review summarizes recent advances in C–S and C–Se formations via transition metal-catalyzed C–H functionalization utilizing directing groups to control the site-selectivity.

Mechanism of Oxidation Reactions of Bromine

1958 ◽  
Vol 14 (5_6) ◽  
pp. 357-360
Author(s):  
K. C. Grover ◽  
R. C. Mehrotra
Keyword(s):  
Oxidation Reactions ◽  
Mechanism Of Oxidation

Mechanism of Oxidation Reactions of Bromine

1958 ◽  
Vol 14 (5_6) ◽  
pp. 345-356 ◽  
Author(s):  
K. C. Grover ◽  
R. C. Mehrotra
Keyword(s):  
Oxidation Reactions ◽  
Mechanism Of Oxidation

Thermo-Oxidative Decomposition of Lovage (Levisticum officinale) and Davana (Artemisia pallens) Essential Oils under Simulated Tobacco Heating Product Conditions

2020 ◽  
Vol 29 (1) ◽  
pp. 27-43
Author(s):  
Emma Jakab ◽  
Zoltán Sebestyén ◽  
Bence Babinszki ◽  
Eszter Barta-Rajnai ◽  
Zsuzsanna Czégény ◽  
...  
Keyword(s):  
Low Temperature ◽  
Essential Oils ◽  
Relative Yield ◽  
Gas Chromatography Mass Spectrometry ◽  
Intramolecular Rearrangement ◽  
Oxidation Reactions ◽  
Pyrolysis Gas ◽  
Oxidative Decomposition ◽  
Oxidative Pyrolysis ◽  
Artemisia Pallens

SummaryThe thermo-oxidative decomposition of lovage (Levisticum officinale) and davana (Artemisia pallens) essential oils has been studied by pyrolysis-gas chromatography/mass spectrometry in 9% oxygen and 91% nitrogen atmosphere at 300 °C to simulate low-temperature tobacco heating conditions. Both lovage and davana oils contain numerous chemical substances; the main components of both oils are various oxygen-containing compounds. Isobenzofuranones are the most important constituents of lovage oil, and their relative intensity changed significantly during oxidative pyrolysis. (Z)-ligustilide underwent two kinds of decomposition reactions: an aromatization reaction resulting in the formation of butylidenephthalide and the scission of the lactone ring with the elimination of carbon dioxide or carbon monoxide. Davanone is the main component of davana oil, which did not decompose considerably during low-temperature oxidative pyrolysis. However, the relative yield of the second most intensive component, bicyclogermacrene, reduced markedly due to bond rearrangement reactions. Davana ether underwent oxidation reactions leading to the formation of various furanic compounds. The changes in the composition of both essential oils could be interpreted in terms of bond splitting, intramolecular rearrangement mechanisms and oxidation reactions of several constituents during low-temperature oxidative pyrolysis. The applied thermo-oxidative method was found to be suitable to study the stability of the essential oils and monitor the decomposition products under simulated tobacco heating conditions. In spite of the complicated composition of the essential oils, no evidence for interaction between the oil components was found. [Beitr. Tabakforsch. Int. 29 (2020) 27–43]

Cobalt/Lewis Acid Catalysis for Hydrocarbofunctionalization of Alkynes via Cooperative C–H Activation

2020 ◽  
Author(s):  
Chang-Sheng Wang ◽  
Sabrina Monaco ◽  
Anh Ngoc Thai ◽  
Md. Shafiqur Rahman ◽  
Chen Wang ◽  
...  
Keyword(s):  
Catalytic System ◽  
Lewis Acid ◽  
Hydrogen Transfer ◽  
Acid Catalysis ◽  
Rate Limiting Step ◽  
Site Selectivity ◽  
Set Up ◽  
Site Selective ◽  
First Time ◽  
Rate Limiting

A catalytic system comprised of a cobalt-diphosphine complex and a Lewis acid (LA) such as AlMe3 has been found to promote hydrocarbofunctionalization reactions of alkynes with Lewis basic and electron-deficient substrates such as formamides, pyridones, pyridines, and azole derivatives through site-selective C-H activation. Compared with known Ni/LA catalytic system for analogous transformations, the present catalytic system not only feature convenient set up using inexpensive and bench-stable precatalyst and ligand such as Co(acac)3 and 1,3-bis(diphenylphosphino)propane (dppp), but also display distinct site-selectivity toward C-H activation of pyridone and pyridine derivatives. In particular, a completely C4-selective alkenylation of pyridine has been achieved for the first time. Mechanistic stidies including DFT calculations on the Co/Al-catalyzed addition of formamide to alkyne have suggested that the reaction involves cleavage of the carbamoyl C-H bond as the rate-limiting step, which proceeds through a ligand-to-ligand hydrogen transfer (LLHT) mechanism leading to an alkyl(carbamoyl)cobalt intermediate.

Imine as a Linchpin Approach for Distal C(sp2)–H Functionalization

2020 ◽  
Author(s):  
Sukdev Bag ◽  
Sadhan Jana ◽  
Sukumar Pradhan ◽  
Suman Bhowmick ◽  
Nupur Goswami ◽  
...  
Keyword(s):  
Organic Molecules ◽  
Bond Activation ◽  
Bond Formation ◽  
Ancillary Ligand ◽  
Significant Challenge ◽  
Site Selectivity ◽  
Directing Group ◽  
Covalently Linked ◽  
Complex Organic ◽  
Post Functionalization

<p>Despite the widespread applications of C–H functionalization, controlling site selectivity remains a significant challenge. Covalently attached directing group (DG) served as an ancillary ligand to ensure proximal <i>ortho</i>-, distal <i>meta</i>- and <i>para</i>-C-H functionalization over the last two decades. These covalently linked DGs necessitate two extra steps for a single C–H functionalization: introduction of DG prior to C–H activation and removal of DG post-functionalization. We introduce here a transient directing group for distal C(<i>sp<sup>2</sup></i>)-H functionalization <i>via</i> reversible imine formation. By overruling facile proximal C-H bond activation by imine-<i>N</i> atom, a suitably designed pyrimidine-based transient directing group (TDG) successfully delivered selective distal C-C bond formation. Application of this transient directing group strategy for streamlining the synthesis of complex organic molecules without any necessary pre-functionalization at the distal position has been explored.</p>

Oxidase Catalysis via an Aerobically Generated Dess-Martin Periodinane Analogue

2018 ◽  
Author(s):  
Asim Maity ◽  
Sung-Min Hyun ◽  
Alan Wortman ◽  
David Powers
Keyword(s):  
Chemical Synthesis ◽  
Aerobic Oxidation ◽  
Substrate Oxidation ◽  
Oxidation Catalysis ◽  
Hypervalent Iodine ◽  
Oxidation Reactions ◽  
Broad Array ◽  
Oxidation Chemistry ◽  
Reactive Oxidants

<p>Hypervalent iodine(V) reagents, such as Dess-Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis. Development of strategies to access these reagents from O2 would immediately enable use of O2 as a terminal oxidant in a broad array of substrate oxidation reactions. Recently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. Here, we couple aerobic oxidation of iodobenzenes with disproportionation of the initially generated I(III) compounds to generate I(V) reagents. The aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP. Further, the developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.</p>

Theoretical and experimental studies of palladium-catalyzed site-selective C(sp3)−H bond functionalization enabled by transient ligands

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Bond Functionalization ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
Site Selective

Transition metal-catalyzed selective C–H bond functionalization enabled by transient ligands has become an extremely attractive topic due to its economical and greener characteristics. However, catalytic pathways of this reaction process on unactivated sp<sup>3</sup> carbons of reactants have not been well studied yet. Herein, detailed mechanistic investigation on Pd-catalyzed C(sp<sup>3</sup>)–H bond activation with amino acids as transient ligands has been systematically conducted. The theoretical calculations showed that higher angle distortion of C(sp2)-H bond over C(sp3)-H bond and stronger nucleophilicity of benzylic anion over its aromatic counterpart, leading to higher reactivity of corresponding C(sp<sup>3</sup>)–H bonds; the angle strain of the directing rings of key intermediates determines the site-selectivity of aliphatic ketone substrates; replacement of glycine with β-alanine as the transient ligand can decrease the angle tension of the directing rings. Synthetic experiments have confirmed that β-alanine is indeed a more efficient transient ligand for arylation of β-secondary carbons of linear aliphatic ketones than its glycine counterpart.<br><br>

Tuning the Activities of Cu2O Nanostructures via the Oxide-Metal Interaction

2019 ◽  
Author(s):  
Wugen Huang ◽  
qingfei liu ◽  
Zhiwen Zhou ◽  
Yangsheng Li ◽  
Yong Wang ◽  
...  
Keyword(s):  
Co Oxidation ◽  
Oxidation Catalysis ◽  
Atomic Scale ◽  
Scanning Tunneling ◽  
Oxidation Reactions ◽  
Tunneling Microscopy ◽  
Temperature Oxidation ◽  
Metal Interaction ◽  
Tremendous Importance ◽  
Oxygen Atoms

Despite tremendous importance in catalysis, the design and improvement of the oxide- metal interface has been hampered by the limited understanding on the nature of interfacial sites, as well as the oxide-metal interaction (OMI). Through the construction of well-defined Cu<sub>2</sub>O-Pt, Cu<sub>2</sub>O-Ag, Cu<sub>2</sub>O-Au interfaces, we found that Cu<sub>2</sub>O Nanostructures (NSs) on Pt exhibit much lower thermal stability than on Ag and Au, although they show the same surface and edge structures, as identified by element-specific scanning tunneling microscopy (ES-STM) images. The activities of the Cu<sub>2</sub>O-Pt and Cu<sub>2</sub>O-Au interfaces for CO oxidation were further compared at the atomic scale and showed in general that the interface with Cu<sub>2</sub>O NSs could annihilate the CO-poisoning problem suffered by Pt group metals and enhance the interaction with O<sub>2</sub>, which is a limiting step for CO oxidation catalysis on group IB metals. While both interfaces could react with CO at room temperature, the OMI was found to determine the reactivity of supported Cu<sub>2</sub>O NSs by 1) tuning the activity of interfacial oxygen atoms and 2) stabilizing oxygen vacancies or vice versa, the dissociated oxygen atoms at the interface. Our study provides new insight for OMI and for the development of Cu-based catalysts for low temperature oxidation reactions.

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