Chloroform-based Atherton–Todd-type reactions of alcohols and thiols with secondary phosphine oxides generating phosphinothioates and phosphinates

RSC Advances ◽  
2015 ◽  
Vol 5 (88) ◽  
pp. 71544-71546 ◽  
Author(s):  
Shan Li ◽  
Tieqiao Chen ◽  
Yuta Saga ◽  
Li-Biao Han
Keyword(s):  
Functional Groups ◽  
Secondary Phosphine ◽  
Phosphine Oxides ◽  
Reaction Conditions

Various valuable phosphinothioates and phosphinates including those with functional groups are readily prepared under mild reaction conditions via chloroform-based Atherton–Todd-type reactions of secondary phosphine oxides with alcohols and thiols, respectively.

Palladium-Catalyzed C–P Cross-Coupling between (Het)aryl Halides and Secondary Phosphine Oxides

Synthesis ◽  
2019 ◽  
Vol 51 (11) ◽  
pp. 2379-2386 ◽  
Author(s):  
Gladis Zakirova ◽  
Dmitrii Mladentsev ◽  
Nataliya Borisova
Keyword(s):  
Electronic Properties ◽  
Heterocyclic Compounds ◽  
Cross Coupling ◽  
Secondary Phosphine ◽  
Phosphine Oxides ◽  
Tertiary Phosphine ◽  
Reaction Conditions ◽  
Efficient Procedure ◽  
Palladium Catalyzed ◽  
Tertiary Alkyl

An efficient procedure for C–P bond formation via the palladium-catalyzed [Pd(OAc)2/dppf/Cs2CO3] reaction between dichloroheterocycles and secondary phosphine oxides was developed. The steric and electronic properties of substituents were varied to establish the scope and limitations of the method developed. By applying these conditions, a variety of new heterocyclic compounds bearing two tertiary phosphine oxides were successfully synthesized in moderate to excellent yields. After adjustments to the reaction conditions [Pd(OAc)2/dippf/t-BuOK], cross-coupling of secondary phosphine oxides with bulky (secondary or tertiary alkyl) substituents on the phosphorus atom was achieved. Extension of the methodology to monohalohetarenes and monohaloarenes was successfully carried out; once again, the steric and electronic properties of the halides were varied widely. The desired reaction occurred in all cases studied, giving high to excellent yields of product regardless of the nature and positions of substituents.

scholarly journals Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes

Organics ◽  
2021 ◽  
Vol 2 (4) ◽  
pp. 395-403
Author(s):  
Toshiaki Murai ◽  
Ryota Wada ◽  
Kouji Iwata ◽  
Yuuki Maekawa ◽  
Kazuma Kuwabara ◽  
...  
Keyword(s):  
Carbon Atom ◽  
Phosphorus Atom ◽  
Organophosphorus Compounds ◽  
Radical Addition ◽  
Secondary Phosphine ◽  
Phosphine Oxides ◽  
Reaction Conditions ◽  
High Yields ◽  
Oxidized Products

Organophosphorus compounds with stereogenic phosphorus and carbon atoms have received increasing attention. In this regards, primary phosphines with a stereogenic carbon atom adjacent to the phosphorus atom were synthesized by the reduction in phosphonates and phosphonoselenoates with a binaphthyl group. Their oxidized products, i.e., phosphine oxides with a stereogenic tetrasubstituted carbon atom, were found to undergo BEt3-mediated radical addition to cyclohexene to give P-stereogenic secondary phosphine oxides with a diastereoselectivity of 91:9. The products were characterized by ordinary analytical methods, such as Fourier transform infrared spectroscopy; 1H, 13C, and 31P NMR spectroscopies; and mass spectroscopy. Computational studies on the phosphorus-centered radical species and the obtained product implied that the thermodynamically stable radical and the adduct may be formed as a major diastereomer. The radical addition to a range of alkenes took place in an anti-Markovnikov fashion to give P-stereogenic secondary phosphine oxides. A variety of functional groups in the alkenes were tolerated under the reaction conditions to afford secondary phosphine oxides in moderate yields. Primary phosphines with an alkenyl group, which were generated in situ, underwent intramolecular cyclization to give five- and six-membered cyclic phosphines in high yields after protection by BH3.

Chemical reduction of chlorpyrifos driven by flavin mononucleotide functionalized titanium (IV) dioxide

2020 ◽  
Vol 5 (11) ◽  
Author(s):  
Stephanie Santos Díaz ◽  
Hazim Al-Zubaidi ◽  
Amir C. Ross-Obare ◽  
Sherine O. Obare
Keyword(s):  
Functional Groups ◽  
Organic Contaminants ◽  
Chemical Reduction ◽  
Flavin Mononucleotide ◽  
Reaction Conditions ◽  
Organophosphate Compounds ◽  
Biological Molecule ◽  
Highly Active ◽  
New Directions ◽  
Detrimental Impact

AbstractFor many decades, organohalide and organophosphate compounds have shown significant detrimental impact on the environment. Consequently, strategies for their remediation continue to be an area of emerging need. The reduction of the chlorpyrifos pesticide, a molecule that bears both organohalide and organophosphate functional groups, is an important area of investigation due to it toxic nature. In this report, we demonstrate the effectiveness of the biological molecule, flavin mononucleotide (FMN) toward chemically reducing chlorpyrifos. The FMN was found to be highly active when anchored to nanocrystalline TiO2 surfaces. The results show new directions toward the remediation of organic contaminants under mild reaction conditions.

Thermal stability of primary and secondary phosphine oxides formed as a reaction of phosphine oxide with ketones

2016 ◽  
Vol 191 (11-12) ◽  
pp. 1480-1481 ◽  
Author(s):  
E. V. Gorbachuk ◽  
E. K. Badeeva ◽  
S. A. Katsyuba ◽  
P. O. Pavlov ◽  
Kh. R. Khayarov ◽  
...  
Keyword(s):  
Thermal Stability ◽  
Phosphine Oxide ◽  
Secondary Phosphine ◽  
Phosphine Oxides ◽  
Thermal Stability Of

Preparation of Optically Pure Tertiary Phosphine Oxides via the Addition ofP-Stereogenic Secondary Phosphine Oxide to Activated Alkenes

2016 ◽  
Vol 81 (17) ◽  
pp. 7644-7653 ◽  
Author(s):  
Ji-Ping Wang ◽  
Shao-Zhen Nie ◽  
Zhong-Yang Zhou ◽  
Jing-Jing Ye ◽  
Jing-Hong Wen ◽  
...  
Keyword(s):  
Phosphine Oxide ◽  
Secondary Phosphine ◽  
Phosphine Oxides ◽  
Tertiary Phosphine ◽  
Optically Pure

scholarly journals Preparation and Characterization of Chemically-Modified Biomaterials and Their Application as Adsorbents of Penicillin G

2018 ◽  
Vol 1 (1) ◽  
pp. 114-124 ◽  
Author(s):  
Jesie Silva ◽  
Lizebel Morante ◽  
Tesfamichael Demeke ◽  
Jacqueline Baah-Twum ◽  
Abel Navarro
Keyword(s):  
Chemical Modification ◽  
Functional Groups ◽  
Negative Impact ◽  
Ph Dependence ◽  
Sem Analysis ◽  
Penicillin G ◽  
Tea Leaves ◽  
Reaction Conditions ◽  
Spent Tea Leaves

The prevalence of antibiotics in water creates microbial resistance and has a negative impact on the ecosystem. Biomaterials such as spent tea leaves are rich in functional groups and are suitable for chemical modification for diverse applications. This research proposes the use of spent tea leaves of chamomile (CM), green tea (GT), and peppermint (PM) as structural scaffolds for the incorporation of carboxyl, sulfonyl, and thiol groups to improve the adsorption of Penicillin G (Pe). Adsorbents characterization reported a higher number of acidic functional groups, mainly in thiolated products. Scanning electron microscopy (SEM) analysis showed changes on the surfaces of the adsorbents due to reaction conditions, with a stronger effect on thiolated and sulfonated adsorbents. Elemental analysis by Energy dispersive X-ray spectrophotometry (EDS) corroborated the chemical modification by the presence of sulfur atoms and the increase in oxygen/carbon ratios. Batch experiments at different pH shows a strong pH-dependence with a high adsorption at pH 8 for all the adsorbents. The adsorption follows the trend CMs > GTs > PMs. Thiolation and sulfonation reported higher adsorptions, which is most likely due to the sulfur bridge formation, reaching adsorption percentages of 25%. These results create a new mindset in the use of spent tea leaves and their chemical modifications for the bioremediation of antibiotics.

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