AI Article Synopsis
- A new reductive amination strategy using InCl3/Et3SiH/MeOH offers a nontoxic, chemoselective method for reacting aldehydes and ketones with various amines.
- The methodology is stable with multiple functional groups (esters, hydroxyls, carboxylic acids, olefins) and operates under mild conditions without water sensitivity.
- NMR and ESI-MS techniques reveal key active species involved in the reaction, showcasing the crucial role of methanol in enabling efficient indium hydride generation at room temperature.
Article Abstract
A new strategy has been developed for reductive amination of aldehydes and ketones with the InCl3/Et3SiH/MeOH system, which is a nontoxic system with highly chemoselective and nonwater sensitive properties. The methodology can be applied to a variety of cyclic, acyclic, aromatic, and aliphatic amines. Functionalities including ester, hydroxyl, carboxylic acid, and olefin are found to be stable under our conditions. The reaction shows a first-order kinetics profile with respect to both InCl3 and Et3SiH. Spectroscopic techniques such as NMR and ESI-MS have been employed to probe the active and resulting species arising from InCl3 and Et3SiH in MeOH, which are important in deriving a mechanistic proposal. In the ESI-MS studies, we have first discovered the existence of stable methanol-coordinated indium(III) species which are presumably responsible for the gentle generation of indium hydride at room temperature. The solvent attribution was crucial in tuning the reactivity of [In-H] species, leading to the establishment of mild reaction conditions. The system is superior in flexible tuning of hydride reactivity, resulting in the system being highly chemoselective.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jo8016082 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
General chemoselective hindered amide coupling enabled by TCFH-catalytic Oxyma and transient imine protection.
Chem Commun (Camb)
December 2024
Process Research & Development, Merck & Co., Inc., Rahway, New Jersey 07065, USA.
We report a general chemoselective strategy for amide bond formation with poorly nucleophilic amines in the presence of reactive primary alcohols or amines as the competing nucleophiles. The selectivity for less reactive amines over competing alcohols was achieved using TCFH and catalytic Oxyma as a highly reactive, inexpensive, and safe reagent combination. By temporarily masking more reactive amines as imines through the use of electron-deficient aldehydes, the hindered amines could be similarly coupled with high efficiency and selectivity.
View Article and Find Full Text PDFCatalytic Reductive Amination and Tandem Amination-Alkylation of Esters Enabled by a Cationic Iridium Complex.
Angew Chem Int Ed Engl
December 2024
Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P. R. China.
Reported herein is a convenient and efficient method for one-pot, catalytic reductive amination, as well as the first multi-component tandem reductive amination-functionalization of bench-stable and readily available common carboxylic esters. This method is based on the cationic [Ir(COD)]BArF-catalyzed chemoselective hydrosilylation of esters, followed by one-pot acid-mediated amination and nucleophilic addition. The reaction was conducted under mild conditions at a very low catalyst loading (0.
View Article and Find Full Text PDFPhosphinothio(seleno)ation of alkynes/olefins and application on the late-stage functionalization of natural products.
Commun Chem
December 2024
State Key Laboratory of Chemical Biology, State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Zhangjiang Hi-Tech Park, Shanghai, China.
Article Synopsis
- Non-metallic catalysis is emerging as an effective approach for the hydrofunctionalization of unsaturated hydrocarbons, utilizing a unique BF·OEt-promoted method.
- The study presents a highly selective and efficient multi-component reaction, characterized by a Markovnikov addition mechanism, validated through various experimental analyses.
- Successful gram-scale application and exploration of drug derivatives indicate the potential of this method in developing new compounds, including one showing promise for anti-Parkinson's disease activity.
Peptide stapling reactions represent powerful methods for structuring native α-helices to improve their bioactivity in targeting protein-protein interactions (PPIs). In light of a growing need for regio- and positionally selective stapling methods involving natural amino acid residues in their unprotected states, we report a rapid, mild, and highly chemoselective three-component stapling reation using a class of molecular linchpins based on 2-arylketobenzaldehydes (ArKBCHOs) that create a fluorescent staple, hereafter referred to as a Fluorescent Isoindole Crosslink (FlICk). This methodology offers positional selectivity favouring , + 4 helical staples comprising a lysine and cysteine, in the presence of competing nucleophiles on unprotected peptides.
View Article and Find Full Text PDFDual Inert C-H Bond Site-Selective Activations Enabled by Pd/Norbornene-Mediated Cascade Cyclization toward Medium-Sized Polyheterocyclic Methylene Sulfoximines.
Org Lett
December 2024
Key Laboratory of Novel Targets and Drug Study for Neural Repair of Zhejiang Province, School of Medicine, Hangzhou City University, Hangzhou 310015, Zhejiang, P. R. China.
A Pd/norbornene-mediated three-component modular one-step reaction facilitated by dual C-H bond activation and cascade cyclization is reported. This procedure uses norbornene as a catalyst in the Catellani-type reaction and as an alkylating building block to accomplish the dual unactivated C-H bond functionalization protocol, which results in the production of polyheterocyclic eight-membered sulfoximines with an indene-fused moiety. This mild, scalable protocol's wide substrate range makes it ideal for site-selective dual C-H functionalization at the highly chemoselective aryl sites.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!