Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Photoinduced iron-catalyzed C-H alkylation of polyolefins.

ABSTRACT: Chemically introducing diverse polar groups into polyolefins via carbon-hydrogen bond alkylation with polar olefins is of substantial value in the synthesis of next-generation lightweight thermoplastics, which is still underdeveloped. In this work, we report a new approach for efficient carbon-hydrogen bond alkylation in commodity polyolefins using photoinduced iron catalysis. Various polyolefins could be functionalized with broad scope. Polar groups could be incorporated in a single step. The controllable synthesis of multi-polar functional polyolefins could be achieved by a designed module-assembled process. Remarkably, even low levels of functionalization could upcycle the polyolefin materials to exhibit unusual physical properties, such as enhancement of the transparencies, strains, stresses at break of the materials, and hydrophilicity.

SUBMITTER: Zhang Z

PROVIDER: S-EPMC10498505 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Photoinduced iron-catalyzed C-H alkylation of polyolefins.

Zhang Zongnan Z Zhang Yanfeng Y Zeng Rong R

Chemical science 20230804 35

Chemically introducing diverse polar groups into polyolefins <i>via</i> carbon-hydrogen bond alkylation with polar olefins is of substantial value in the synthesis of next-generation lightweight thermoplastics, which is still underdeveloped. In this work, we report a new approach for efficient carbon-hydrogen bond alkylation in commodity polyolefins using photoinduced iron catalysis. Various polyolefins could be functionalized with broad scope. Polar groups could be incorporated in a single step ...[more]

PMID: 37712034

Similar Datasets

The power of microdroplet photochemistry† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4sc00056k

Project description: Not available

| S-EPMC10915808 | biostudies-literature

Total synthesis of bi-magnolignan† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3ra01121f

Project description:Bi-magnolignan, isolated from the leaves of Magnolia officinalis, has shown excellent physiological activity against tumor cells. An efficient strategy for the first total synthesis of bi-magnolignan is reported. The bi-dibenzofuran skeleton was constructed via functional group interconversions of commercially available materials 1,2,4-trimethoxybenzene and 4-allylanisole. Then, the dibenzofuran skeleton was afforded by subsequent Suzuki coupling and intramolecular dehydration. The total synthesis of natural product was accomplished through FeCl3 catalyzed oxidative coupling. The first total synthesis of bi-magnolignan in eight steps from commercially available starting materials has been developed.

| S-EPMC10018648 | biostudies-literature

Photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated olefins with aryl bromides† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4sc03355h

Project description: Not available

| S-EPMC11342154 | biostudies-literature

Alkylboronic acids as alkylating agents: photoredox-catalyzed alkylation reactions assisted by K3PO4† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d2sc05521j

Project description:Despite the ubiquity of alkylboronic acids in organic synthesis, their utility as alkyl radical precursors in visible-light-induced photocatalytic reactions is limited by their high oxidation potentials. In this study, we demonstrated that an inorganophosphorus compound can modulate the oxidation potentials of alkylboronic acids so that they can act as alkyl radical precursors. We propose a mechanism based on the results of fluorescence quenching experiments, electrochemical experiments, 11B and 31P NMR spectroscopy, and other techniques. In addition, we describe a simple and reliable alkylation method that has good functional group tolerance and can be used for direct C–B chlorination, cyanation, vinylation, alkynylation, and allylation, as well as late-stage functionalization of derivatized drug molecules. Notably, alkylboronic acids can be selectively activated in the presence of a boronic pinacol ester. An alkylation method using inorganophosphorus-activated alkylboronic acids to act as alkyl radical precursors has been developed. This method can be used for direct C–B chlorination, cyanation, vinylation, alkynylation, and allylation.

| S-EPMC9683010 | biostudies-literature

Boric acid catalysed hydrolysis of peroxyacids† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3ra01046e

Project description:This study shows for the first time that boric acid catalyses the hydrolysis of peroxyacids, resulting in an approximately 12-fold increase in hydrolysis rate for both peracetic acid (PAA) and 3-chloroperbenzoic acid (MCPBA) when 0.1 M boric acid is present. The maximum rate of hydrolysis occurs at pH 9 and pH 8.4 for PAA and MCPBA respectively. In contrast, carbonate buffer does not enhance the rate of PAA hydrolysis. The reaction was followed by measuring the initial rate of hydrogen peroxide formation using a specific Ti(iv) complexation method. The study of the hydrolysis reaction requires the presence of 2 × 10−5 M each of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine tetramethylene phosphonic acid (EDTMP) in all solutions in order to chelate metal ions across the full pH range (3 to 13) that would otherwise contribute to peroxyacid decomposition. Catalysis of peroxyacid hydrolysis is most likely effected by the triganol boric acid acting as a Lewis acid catalyst, associating with the peroxide leaving group in the transition state to reduce the leaving group basicity. The products of the reaction are the well characterised monoperoxoborate species and the parent carboxylic acid. Analysis of the pH and borate dependence data reveals that in addition to a catalytic pathway involving a single boric acid molecule, there is a significant pathway involving either (a) two boric acid molecules or (b) the polyborate species, B3O3(OH)4−. Knowledge about catalytic mechanisms for the loss of peroxyacids through hydrolysis is important because they are widely used in reagents in a range of oxidation, bleaching and disinfection applications. Boric acid catalyses the hydrolysis of peroxyacids, with possible pathways involving one and two molecules of boric acid as well as polyborate species.

| S-EPMC10103745 | biostudies-literature

AI facilitated fluoro-electrochemical phytoplankton classification† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3sc01741a

Project description:Marine phytoplankton is extremely diverse. Counting and characterising phytoplankton is essential for understanding climate change and ocean health not least since phytoplankton extensively biomineralize carbon dioxide whilst generating 50% of the planet's oxygen. We report the use of fluoro-electrochemical microscopy to distinguish different taxonomies of phytoplankton by the quenching of their chlorophyll-a fluorescence using chemical species oxidatively electrogenerated in situ in seawater. The rate of chlorophyll-a quenching of each cell is characteristic of the species-specific structural composition and cellular content. But with increasing diversity and extent of phytoplankton species under study, human interpretation and distinction of the resulting fluorescence transients becomes increasingly and prohibitively difficult. Thus, we further report a neural network to analyse these fluorescence transients, with an accuracy >95% classifying 29 phytoplankton strains to their taxonomic orders. This method transcends the state-of-the-art. The success of the fluoro-electrochemical microscopy combined with AI provides a novel, flexible and highly granular solution to phytoplankton classification and is adaptable for autonomous ocean monitoring. Schematic of fluoro-electrochemical microscopy. (a) Cartoon E. huxleyi is green under normal light, but (b) emits red fluorescence under UV. (c) Placed near an oxidizing electrode, its fluorescence fades and ultimately (d) “switches off”.

| S-EPMC10246652 | biostudies-literature

Electrically conductive [Fe4S4]-based organometallic polymers† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d3sc02195e

Project description: Not available

| S-EPMC10599474 | biostudies-literature

Concise two-step chemical synthesis of molnupiravir† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d2ra05064a

Project description:A concise synthesis of molnupiravir in a one-pot two-step approach starting from uridine is described. Formally, herein, two sets of one-pot two-reaction steps introducing simplicity for purifications and using chemically available reagents are presented. In this context, molnupiravir was obtained in up to 68% overall yield and multigram-scale. In addition, HPLC analysis showed the molnupiravir purity above 99%. Fast, effective and chromatography column-free chemical synthesis of molnupiravir.

| S-EPMC9585438 | biostudies-literature

Deaminative coupling of benzylamines and arylboronic acids† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d2sc06055h

Project description:A metal-free deaminative coupling of non-prefunctionalised benzylamines and arylboronic acids is reported. In this operationally simple reaction, a primary amine in benzylamine is converted into a good leaving group in situ using inexpensive and commercially available isoamyl nitrite as a nitrosating reagent. Lewis-acidic arylboronic acids are shown to replace mineral acids such as HCl or HBF4 that are conventionally used in the preparation of aryl diazonium salts. This unlocked the formation of the corresponding diarylmethanes by forging a new C–C bond in good yields. A metal-free deaminative coupling of non-prefunctionalised benzylamines and arylboronic acids is reported.

| S-EPMC9930926 | biostudies-literature

Pathway-dependent supramolecular polymerization by planarity breaking† † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4sc02499k

Project description: Not available

| S-EPMC11253169 | biostudies-literature