Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Sustainable Asymmetric Organolithium Chemistry: Enantio- and Chemoselective Acylations through Recycling of Solvent, Sparteine, and Weinreb "Amine".

ABSTRACT: The well-established Hoppe-Beak chemistry, which involves enantioselective generation of organolithium compounds in the presence of (-)-sparteine, was revisited and applied to unprecedented acylations with Weinreb amides to access highly enantioenriched ?-oxyketones and cyclic ?-aminoketones. Recycling of the sustainable solvent cyclopentyl methyl ether, sparteine, and the released Weinreb "amine" [HNMe(OMe)] was possible through a simple work-up procedure that enabled full recovery of these precious materials. The methodology features a robust scope and flexibility, thus allowing the enantioselective preparation of scaffolds amenable of further derivatization.

SUBMITTER: Monticelli S

PROVIDER: S-EPMC6704367 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Sustainable Asymmetric Organolithium Chemistry: Enantio- and Chemoselective Acylations through Recycling of Solvent, Sparteine, and Weinreb "Amine".

Monticelli Serena S Holzer Wolfgang W Langer Thierry T Roller Alexander A Olofsson Berit B Pace Vittorio V

ChemSusChem 20190213 6

The well-established Hoppe-Beak chemistry, which involves enantioselective generation of organolithium compounds in the presence of (-)-sparteine, was revisited and applied to unprecedented acylations with Weinreb amides to access highly enantioenriched α-oxyketones and cyclic α-aminoketones. Recycling of the sustainable solvent cyclopentyl methyl ether, sparteine, and the released Weinreb "amine" [HNMe(OMe)] was possible through a simple work-up procedure that enabled full recovery of these pre ...[more]

PMID: 30614208

Similar Datasets

Studies on the Bisoxazoline and (-)-Sparteine Mediated Enantioselective Addition of Organolithium Reagents to Imines.

Project description:The enantioselective addition of organolithium reagents to N-anisyl aldimines promoted by chiral bisoxazolines and (-)-sparteine as external ligands is described. This reaction proceeds readily with a wide range of aldimine substrates (aliphatic, aromatic, olefinic) and organolithium nucleophiles (Me, n-Bu, Ph, vinyl) in excellent yields (81-99%) and with high enantioselectivities (up to 95.5:4.5 er). The external ligands can be used in substoichiometric amounts albeit with slightly attenuated enantioselectivities. A systematic evaluation of the structural features of the bisoxazolines revealed a primary contribution from the substituent at C(4) and a secondary influence from the bridging substituents. A computational analysis (PM3) provided a clear rationalization for the origin of enantioselectivity.

| S-EPMC2756708 | biostudies-other

Chemoselective Installation of Amine Bonds on Proteins through Aza-Michael Ligation.

Project description:Chemical modification of proteins is essential for a variety of important diagnostic and therapeutic applications. Many strategies developed to date lack chemo- and regioselectivity as well as result in non-native linkages that may suffer from instability in vivo and adversely affect the protein's structure and function. We describe here the reaction of N-nucleophiles with the amino acid dehydroalanine (Dha) in a protein context. When Dha is chemically installed in proteins, the addition of a wide-range N-nucleophiles enables the rapid formation of amine linkages (secondary and tertiary) in a chemoselective manner under mild, biocompatible conditions. These new linkages are stable at a wide range of pH values (pH 2.8 to 12.8), under reducing conditions (biological thiols such as glutathione) and in human plasma. This method is demonstrated for three proteins and is shown to be fully compatible with disulfide bridges, as evidenced by the selective modification of recombinant albumin that displays 17 structurally relevant disulfides. The practicability and utility of our approach is further demonstrated by the construction of a chemically modified C2A domain of Synaptotagmin-I protein that retains its ability to preferentially bind to apoptotic cells at a level comparable to the native protein. Importantly, the method was useful for building a homogeneous antibody-drug conjugate with a precise drug-to-antibody ratio of 2. The kinase inhibitor crizotinib was directly conjugated to Dha through its piperidine motif, and its antibody-mediated intracellular delivery results in 10-fold improvement of its cancer cell-killing efficacy. The simplicity and exquisite site-selectivity of the aza-Michael ligation described herein allows the construction of stable secondary and tertiary amine-linked protein conjugates without affecting the structure and function of biologically relevant proteins.

| S-EPMC5799870 | biostudies-literature

Small Scale and Sustainable Household GreyWater Recycling

Project description:Constructed wetlands for single household greywater treatment and metagenomic analysis of microbes in CWs.

| PRJEB33659 | ENA

Mechanochemical Friedel-Crafts acylations.

Project description:Friedel-Crafts (FC) acylation reactions were exploited in the preparation of ketone-functionalized aromatics. Environmentally more friendly, solvent-free mechanochemical reaction conditions of this industrially important reaction were developed. Reaction parameters such as FC catalyst, time, ratio of reagents and milling support were studied to establish the optimal reaction conditions. The scope of the reaction was explored by employment of different aromatic hydrocarbons in conjunction with anhydrides and acylation reagents. It was shown that certain FC-reactive aromatics could be effectively functionalized by FC acylations carried out under ball-milling conditions without the presence of a solvent. The reaction mechanism was studied by in situ Raman and ex situ IR spectroscopy.

| S-EPMC6604704 | biostudies-literature

Solvent composition regulates the Se : Sb ratio in antimony selenide nanowires deposited from thiol-amine solvent mixtures.

Project description:Antimony selenide (Sb2Se3), a V2VI3 semiconductor with an intriguing crystal structure, has demonstrated improved power conversion and solar-to-hydrogen efficiencies in recent years. Depositing antimony selenide nanowires (NWs) from a solution such as a thiol : amine "alkahest" ink is a low-cost and facile route to deposit high surface area photocathodes. However, little is known about the correlations between the solvent composition and the crystallites' structure and optoelectronic properties, which are crucial for photovoltaic and photoelectrochemical applications. We found that the Se : Sb ratio in the NWs decreases from 3 : 2 to less than 1 : 1 with decreasing thiol : amine ratio in the ink used for deposition but not in the solvent mixture used for dissolving the metals. The reduced Se : Sb ratio in the solid NWS correlates with an optical bandgap wider by ∼0.3 eV in comparison to stoichiometric NWs, a decrease of the NWs diameter from 180 to 30 nanometers, and a ∼0.2 eV larger work function. In addition, we found that the Se : Sb ratio is not uniform along the NWs, which causes a surface potential increase near the tips of the NWs due to a lower Se : Sb ratio near the NWs tips. The increased surface potential near the tips corresponds to a driving force, due to doping or graded bandgap broadening, that facilitates the migration of photoexcited electrons towards the NW tips. Our findings unlock a path for fine-tuning the optoelectronic properties of antimony selenide towards improving the performance of antimony selenide solar cells and photocathodes.

| S-EPMC9419773 | biostudies-literature

Reducing Solvent Consumption in Reductive Catalytic Fractionation through Lignin Oil Recycling.

Project description:Reductive catalytic fractionation (RCF) enables the simultaneous valorization of lignin and carbohydrates in lignocellulosic biomass through solvent-based lignin extraction, followed by depolymerization and catalytic stabilization of the extracted lignin. Process modeling has shown that the use of exogenous organic solvent in RCF is a challenge for economic and environmental feasibility, and previous works proposed that lignin oil, a mixture of lignin-derived monomers and oligomers produced by RCF, can be used as a cosolvent in RCF. Here, we further explore the potential of RCF solvent recycling with lignin oil, extending the feasible lignin oil concentration in the solvent to 100 wt %, relative to the previously demonstrated 0-19 wt % range. Solvents containing up to 80 wt % lignin oil exhibited 83-93% delignification, comparable to 83% delignification with a methanol-water mixture, and notably, using lignin oil solely as a solvent achieved 67% delignification in the absence of water. In additional experiments, applying the RCF solvent recycling approach to ten consecutive RCF reactions resulted in a final lignin oil concentration of 11 wt %, without detrimental impacts on lignin extraction, lignin oil molar mass distribution, aromatic monomer selectivity, and cellulose retention. Overall, this work further demonstrates the potential for using lignin oil as an effective cosolvent in RCF, which can reduce the burden on downstream solvent recovery.

| S-EPMC11351702 | biostudies-literature

Shallow subsurface heat recycling is a sustainable global space heating alternative.

Project description:Despite the global interest in green energy alternatives, little attention has focused on the large-scale viability of recycling the ground heat accumulated due to urbanization, industrialization and climate change. Here we show this theoretical heat potential at a multi-continental scale by first leveraging datasets of groundwater temperature and lithology to assess the distribution of subsurface thermal pollution. We then evaluate subsurface heat recycling for three scenarios: a status quo scenario representing present-day accumulated heat, a recycled scenario with ground temperatures returned to background values, and a climate change scenario representing projected warming impacts. Our analyses reveal that over 50% of sites show recyclable underground heat pollution in the status quo, 25% of locations would be feasible for long-term heat recycling for the recycled scenario, and at least 83% for the climate change scenario. Results highlight that subsurface heat recycling warrants consideration in the move to a low-carbon economy in a warmer world.

| S-EPMC9270455 | biostudies-literature

Sustainable cannabinoids purification through twin-column recycling chromatography and green solvents.

Project description:In the present study, twin-column recycling chromatography has been employed for the purification of a Cannabis extract by using a green solvent, ethanol, as the mobile phase. In particular, the complete removal of the psychoactive tetrahydrocannabinol (THC) from a Cannabis extract rich in cannabidiol (CBD) was achieved under continuous conditions. The performance of the method, in terms of compound purity, recovery, productivity and solvent consumption, was compared to that of traditional batch operations showing the potential of the twin-column recycling approach. The employment of a theoretical model to predict the band profiles of the two compounds during the recycling process has facilitated method development, thus further contributing to process sustainability by avoiding trial and error attempts or at least decreasing the number of steps significantly.

| S-EPMC11249647 | biostudies-literature

A sustainable approach to cathode delamination using a green solvent.

Project description:Designing an environment-friendly delamination process for an end-of-life (EoL) composite cathode is a crucial step in direct cathode recycling. In this study, the green solvent dimethyl isosorbide (DMI) is explored to extract cathode active materials (AMs) from the Al current collector via dissolving the polyvinylidene fluoride (PVDF) binder. Mechanistic insight suggests that binder removal from the Al substrate proceeds via reducing polymer interchain interaction through DMI penetrating into the PVDF crystalline region. Polymer-solvent interaction may increase via establishing hydrogen bond between PVDF and DMI, which facilitates binder removal. Analytical characterizations including 1H NMR, FTIR, XRD and SEM-EDS reveal that the molecular, micro, and crystal structures of the recovered cathode AMs, PVDF and Al foil are preserved. This finding is expected to provide a replacement for the toxic organic solvent N-methylpyrrolidone (NMP) and offers an effective, ecofriendly, and sustainable direct cathode recycling approach for spent Li-ion batteries.

| S-EPMC9037836 | biostudies-literature

Solvent-dependent chemoselective synthesis of different isoquinolinones mediated by the hypervalent iodine(III) reagent PISA.

Project description:Isoquinolinone is an important heterocyclic framework in natural products and biologically active molecules, and the efficient synthesis of this structural motif has received much attention in recent years. Herein, we report a (phenyliodonio)sulfamate (PISA)-mediated, solvent-dependent synthesis of different isoquinolinone derivatives. The method provides highly chemoselective access to 3- or 4-substituted isoquinolinone derivatives by reacting o-alkenylbenzamide derivatives with PISA in either acetonitrile or wet hexafluoro-2-isopropanol.

| S-EPMC11318619 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data