Browse
Submit Data
Databases
API
Help

Dataset Information

23 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Efficient access to aliphatic esters by photocatalyzed alkoxycarbonylation of alkenes with alkyloxalyl chlorides.

ABSTRACT: Aliphatic esters are essential constituents of biologically active compounds and versatile chemical intermediates for the synthesis of drugs. However, their preparation from readily available olefins remains challenging. Here, we report a strategy to access aliphatic esters from olefins through a photocatalyzed alkoxycarbonylation reaction. Alkyloxalyl chlorides, generated in situ from the corresponding alcohols and oxalyl chloride, are engaged as alkoxycarbonyl radical fragments under photoredox catalysis. This transformation tolerates a broad scope of electron-rich and electron-deficient olefins and provides the corresponding β-chloro esters in good yields. Additionally, a formal β-selective alkene alkoxycarbonylation is developed. Moreover, a variety of oxindole-3-acetates and furoindolines are prepared in good to excellent yields. A more concise formal synthesis of (±)-physovenine is accomplished as well. With these strategies, a wide range of natural-product-derived olefins and alkyloxalyl chlorides are also successfully employed.

SUBMITTER: Chen JQ

PROVIDER: S-EPMC8423752 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Highly active and efficient catalysts for alkoxycarbonylation of alkenes.

Project description:Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h-1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product.

| S-EPMC5288498 | biostudies-literature

Rh-catalyzed alkoxycarbonylation of unactivated alkyl chlorides.

Project description:A general rhodium-catalyzed selective carbonylative coupling of unactivated alkyl chlorides with aliphatic alcohols or phenols to the corresponding esters is presented for the first time. Crucial for this transformation is the addition of sodium iodide, which provides in situ more active alkyl iodides. In the presence of a Rh(i)-DPPP catalyst system diverse esters (81 examples) including industrially relevant acetates from chloro- and dichloromethane can be prepared in a straightforward manner in up to 95% isolated yield. The used ligand not only affects the selectivity of the carbonylation reaction but also controls the selectivity of the preceding halide exchange step.

| S-EPMC9682885 | biostudies-literature

Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes.

Project description:Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic and diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cleavage. Subsequent Cl• radical migration forms a localized triplet 1,3-diradical intermediate that, after intersystem crossing, undergoes ring-closing to form the desired product. The mild reaction conditions are compatible with a broad range of functional groups to generate chlorocyclopropanes in high yields and diastereoselectivities. A more efficient process is developed by addition of a catalytic amount of a nickel complex, and we propose a novel role for this cocatalyst to recycle an allyl chloride byproduct generated in the course of the reaction. The reaction is also shown to be stereoconvergent, as an E/Z mixture of cinnamyl chlorides furnish the anti-chlorocyclopropane product in high diastereoselectivity. We anticipate that the use of a visible light activated photocatalyst to transform substrates in combination with a transition metal catalyst to recycle byproducts back into the catalytic cycle will provide unique opportunities for the discovery of new reactivity.

| S-EPMC7224234 | biostudies-literature

Copper-Photocatalyzed Hydroboration of Alkynes and Alkenes.

Project description:The photocatalytic hydroboration of alkenes and alkynes is reported. The use of newly-designed copper photocatalysts with B2 Pin2 permits the formation a boryl radical, which is used for hydroboration of a large panel of alkenes and alkynes. The hydroborated products were isolated in high yields, with excellent diastereoselectivities and a high functional group tolerance under mild conditions. The hydroboration reactions were developed under continuous flow conditions to demonstrate their synthetic utility. The reaction mechanism was studied and suggested an oxidation reaction between an in situ formed borate and the Cu-photocatalyst in its excited state for the boryl radical formation.

| S-EPMC8252632 | biostudies-literature

Asymmetric Enzymatic Hydration of Unactivated, Aliphatic Alkenes.

Project description:The direct enantioselective addition of water to unactivated alkenes could simplify the synthesis of chiral alcohols and solve a long-standing challenge in catalysis. Here we report that an engineered fatty acid hydratase can catalyze the asymmetric hydration of various terminal and internal alkenes. In the presence of a carboxylic acid decoy molecule for activation of the oleate hydratase from E. meningoseptica, asymmetric hydration of unactivated alkenes was achieved with up to 93 % conversion, excellent selectivity (>99 % ee, >95 % regioselectivity), and on a preparative scale.

| S-EPMC6471033 | biostudies-literature

Copper-Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides.

Project description:A method for the copper-catalyzed borylacylation of activated alkenes is presented. The reaction involves borylcupration of the alkene, followed by capture of the generated alkyl-copper intermediate with an acid chloride. The reactions operated with low catalyst loading and generally occurre within 15?min at room temperature for a range of activated alkenes. In the case of vinyl arenes, enantioselective borylacylation was possible.

| S-EPMC5708594 | biostudies-literature

Palladium-Catalyzed Selective Amino- and Alkoxycarbonylation of Iodoarenes with Aliphatic Aminoalcohols as Heterobifunctional O,N-Nucleophiles.

Project description:Palladium-catalyzed amino- and alkoxycarbonylation reactions of aryl iodides were investigated in the presence of aliphatic heterobifunctional N,O-nucleophiles. Selective synthesis of amide alcohols and amide esters was realized, controlled by the base and substrate ratio. The effect of iodobenzene substituents was also studied with surprising results in terms of product selectivity. In addition to the model ethanolamine/iodobenzene system, various heteroaromatic substrates and numerous related nucleophiles were tested under optimized conditions, providing moderate to good yields of the target compounds. Reactions of serinol and 1,3-diamino-2-propanol as model trifunctional compounds showed particularly high chemoselectivity on amide ester products. Considering the coordinative properties of the applied nucleophiles, a rational catalytic cycle was proposed.

| S-EPMC10127279 | biostudies-literature

Regioselective aerobic oxidative Heck reactions with electronically unbiased alkenes: efficient access to α-alkyl vinylarenes.

Project description:Branched-selective oxidative Heck coupling reactions have been developed between arylboronic acids and electronically unbiased terminal alkenes. The reactions exhibit high catalyst-controlled regioselectivity favoring the less common branched isomer. The reactions employ a catalyst composed of Pd(TFA)2/dmphen (TFA = trifluoroacetate, dmphen = 2,9-dimethyl-1,10-phenanthroline) and proceed efficiently at 45-60 °C under 1 atm of O2 without requiring other additives. A broad array of functional groups, including aryl halide, allyl silane and carboxylic acids are tolerated.

| S-EPMC4522933 | biostudies-literature

Nickel-Catalyzed Defluorinative Coupling of Aliphatic Aldehydes with Trifluoromethyl Alkenes.

Project description:A simple procedure is reported for the nickel-catalyzed defluorinative alkylation of unactivated aliphatic aldehydes. The process involves the catalytic reductive union of trifluoromethyl alkenes with aldehydes using a nickel complex of a 6,6'-disubstituted bipyridine ligand with zinc metal as the terminal reductant. The protocol is distinguished by its broad substrate scope, mild conditions, and simple catalytic setup. Reaction outcomes are consistent with the intermediacy of an α-silyloxy(alkyl)nickel intermediate generated by a low-valent nickel catalyst, silyl electrophile, and the aldehyde substrate. Mechanistic findings with cyclopropanecarboxaldehyde provide insights into nature of the reactive intermediates and illustrate fundamental reactivity differences that are governed by subtle changes in ligand and substrate structure.

| S-EPMC9390876 | biostudies-literature

Gold-catalyzed Fluorination of Alkynyl Esters and Ketones: Efficient Access to Fluorinated 1,3-Dicarbonyl Compounds.

Project description:We developed an efficient synthesis of 2-fluoro-1,3-dicarbonyl compounds using readily available alkynyl ketones or esters as starting material. The key step is the insertion of hydrogen fluoride (HF) to the gold carbene intermediate generated from cationic gold catalyzed addition of N-oxides to alkynyl ketones or esters. This method gives excellent chemical yields and regioselectivity with good functional group tolerance.

| S-EPMC5824727 | 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