Browse
Submit Data
Databases
API
Help

Dataset Information

24 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Titanocene(III)-Catalyzed Precision Deuteration of Epoxides.

ABSTRACT: We describe a titanocene(III)-catalyzed deuterosilylation of epoxides that provides β-deuterated anti-Markovnikov alcohols with excellent D-incorporation, in high yield, and often excellent diastereoselectivity after desilylation. The key to the success of the reaction is a novel activation method of Cp₂ TiCl₂ and (tBuC₅ H₄ )₂ TiCl₂ with BnMgBr and PhSiD₃ to provide [(RC₅ H₄ )₂ Ti(III)D] without isotope scrambling. It was developed after discovering an off-cycle scrambling with the previously described method. Our precision deuteration can be applied to the synthesis of drug precursors and highlights the power of combining radical chemistry with organometallic catalysis.

SUBMITTER: Henriques DSG

PROVIDER: S-EPMC9305931 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Titanocene(III)-catalyzed formation of indolines and azaindolines.

Project description:Reductive cyclization of epoxides tethered to substituted anilines and aminopyridines in the presence of 3 mol % of titanocene dichloride and stoichiometric manganese metal promotes a radical annulation to form 3,3-disubstituted indolines and azaindolines.

| S-EPMC5467310 | biostudies-literature

Copolymerization of Phthalic Anhydride with Epoxides Catalyzed by Amine-Bis(Phenolate) Chromium(III) Complexes.

Project description:The effect of ligand structure on the catalytic activity of amine-bis(phenolate) chromium(III) complexes in the ring-opening copolymerization of phthalic anhydride and a series epoxides was studied. Eight complexes differing in the donor-pendant group (R1) and substituents (R2) in phenolate units were examined as catalysts of the model reaction between phthalic anhydride and cyclohexane oxide in toluene. They were used individually or as a part of the binary catalytic systems with nucleophilic co-catalysts. The co-catalyst was selected from the following organic bases: PPh3, DMAP, 1-butylimidazole, or DBU. The binary catalytic systems turned out to be more active than the complexes used individually, and DMAP proved to be the best choice as a co-catalyst. When the molar ratio of [PA]:[epoxide]:[Cr]:[DMAP] = 250:250:1:1 was applied, the most active complex (R1-X = CH2NMe2, R2 = F) allowed to copolymerize phthalic anhydride with differently substituted epoxides (cyclohexene oxide, 4-vinylcyclohexene oxide, styrene oxide, phenyl glycidyl ether, propylene oxide, butylene oxide, and epichlorohydrin) within 240 min at 110 °C. The resulting polyesters were characterized by Mn up to 20.6 kg mol-1 and narrow dispersity, and they did not contain polyether units.

| S-EPMC8197922 | biostudies-literature

Visible-light-driven spirocyclization of epoxides <i>via</i> dual titanocene and photoredox catalysis.

Project description:We describe the synergistic utilization of titanocene/photoredox dual catalysis driven by visible light for the radical opening/spirocyclization of easily accessible epoxyalkynes. This environmentally benign process uses the organic donor-acceptor fluorophore 2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) as a photocatalyst and Hantzsch ester (HE) as an electron donor instead of stoichiometric metallic reductants. The photocatalytic conditions showed exceptionally high reactivity for the synthesis of privileged and synthetically challenging spirocycles featuring a spiro all-carbon quaternary stereocenter. Cyclic voltammetry (CV) studies suggest that Cp2TiIIICl is the catalytically active species.

| S-EPMC8146098 | biostudies-literature

Exploring Short and Efficient Synthetic Routes Using Titanocene(III)-Catalyzed Reactions: Total Synthesis of Natural Meroterpenes with Trisubstituted Unsaturations.

Project description:The stereo- and regioselective total syntheses of OMe derivatives of the scarce bioactive meroterpenoids makassaric acid (1) and fascioquinol B (2) have been accomplished. The synthetic sequences are based on the following three efficient and selective catalytic reactions: Cu-catalyzed addition of Grignard compounds to an epoxide; a regioselective Barbier-type reaction, catalyzed by Cp2TiCl; and regio- and stereoselective bioinspired cyclization, also catalyzed by Cp2TiCl. These three key processes allow us to obtain the main skeletons of 1 and 2 in a few steps. The valuable synthetic proposal shown in this work provides fast access to scarce, structurally complex meroterpenes with promising biological activities, which are a sustainable source for later studies and applications in medicine.

| S-EPMC9031794 | biostudies-literature

Silver-catalyzed regioselective deuteration of (hetero)arenes and α-deuteration of 2-alkyl azaarenes.

Project description:A simple silver-catalyzed regioselective deuteration of (hetero)arenes and α-deuteration of 2-alkyl azaarenes has been described. This strategy provides an efficient and practical avenue to access various deuterated electron-rich arenes, azaarenes and α-deuterated 2-alkyl azaarenes with good to excellent deuterium incorporation utilizing D2O as the source of deuterium atoms.

| S-EPMC9055237 | biostudies-literature

Photoredox-catalyzed deuteration and tritiation of pharmaceutical compounds.

Project description:Deuterium- and tritium-labeled pharmaceutical compounds are pivotal diagnostic tools in drug discovery research, providing vital information about the biological fate of drugs and drug metabolites. Herein we demonstrate that a photoredox-mediated hydrogen atom transfer protocol can efficiently and selectively install deuterium (D) and tritium (T) at α-amino sp3 carbon-hydrogen bonds in a single step, using isotopically labeled water (D2O or T2O) as the source of hydrogen isotope. In this context, we also report a convenient synthesis of T2O from T2, providing access to high-specific-activity T2O. This protocol has been successfully applied to the high incorporation of deuterium and tritium in 18 drug molecules, which meet the requirements for use in ligand-binding assays and absorption, distribution, metabolism, and excretion studies.

| S-EPMC5907472 | biostudies-literature

Photoredox-Catalyzed Enantioselective α-Deuteration of Azaarenes with D2O.

Project description:The site-specific incorporation of deuterium (D) into small molecules is frequently used to access isotopically labeled compounds with broad utility in many research areas, such as drug development, mechanistic studies, and NMR analyses. Nevertheless, the deuteration of a stereocenter in an enantioselective manner, which could slow the metabolism and improve the bioavailability of bioactive molecules, remains challenging owing to the lack of established catalytic methods. Here, we report an asymmetric α-deuteration strategy for azaarenes with inexpensive D2O as the deuterium source. A cooperative visible light-driven photoredox and chiral Brønsted acid-catalyzed system using a Hantzsch ester as the terminal reductant has been developed, which enables racemic α-chloro-azaarenes and prochiral azaarene-substituted ketones to experience a single-electron reduction-enantioselective deuteration process. The transition metal-free method provides important chiral α-deuterated azaarenes in satisfactory yields with good to excellent enantioselectivities (up to 99% ee) and substantial deuterium incorporation.

| S-EPMC6593145 | biostudies-other

Gold(I)-catalyzed cascade cyclization of allenyl epoxides.

Project description:Cationic gold(I) phosphite catalysts activate allenes for epoxide cascade reactions. The system is tolerant of numerous functional groups (sulfones, esters, ethers, sulfonamides) and proceeds at room temperature in dichloromethane. The cyclization pathway is sensitive to the substitution pattern of the epoxide and the backbone structure of the A-ring. It is capable of producing medium-ring ethers, fused 6-5 bicyclic, and linked pyran-furan structures. The resulting cycloisomers are reminiscent of structures found in numerous polyether natural products.

| S-EPMC2742359 | biostudies-literature

Direct coupling of CO<sub>2</sub> with epoxides catalyzed by lanthanum(III) supported on magnetic mesoporous organosilica nanoparticles.

Project description:Lanthanum(III) supported on the magnetic mesoporous organosilica nanoparticle (La@MON) has been described as an efficient, simple, and durable heterogeneous catalyst for the synthesis of 5-membered cyclic carbonates from carbon dioxide (CO2) and epoxides. Under optimized reaction conditions, various terminal epoxides have been converted to the corresponding carbonates in the presence of 0.3 mol% La@MON and 0.5 mol% tetrabutylammonium iodide (TBAI) as co-catalyst at relatively mild reaction conditions. It was also found that La@MON catalysts had significantly higher catalytic activity than some selected reference catalysts, which can be explained by the abundance of lanthanum(III) species acting as Lewis acidic sites for activating both carbon dioxide and epoxide molecules, along with the fact that the catalyst channels are short and provided facile mass transfer. The catalyst showed good reusability for at least five reaction cycles while the magnetic core of the catalyst helps the easy separation of the catalyst by just using an external magnet.

| S-EPMC10073222 | biostudies-literature

Cu-Catalyzed Cross-Coupling of Benzylboronic Esters and Epoxides.

Project description:A reaction between epoxides and benzylboronic acid pinacol esters is described. CuI was found to be an effective catalyst of this transformation upon activation of the benzylboronic ester with an alkyllithium reagent. The reaction was very efficient and a variety of substituted epoxides were found to be good substrates with good regioselectivity for substitution at the less substituted side of the epoxide. A reaction using an enantioenriched secondary benzylboronic ester was found to not be stereospecific.

| S-EPMC8516127 | 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