Methylated amines are highly important for a variety of pharmaceutical and agrochemical applications. Existing routes for their formation result in the production of large amounts of waste or require high reaction temperatures, both of which impact the ecological and economical footprint of the methodologies. Herein, we report the ruthenium-catalyzed reductive methylation of a range of aliphatic amines, using paraformaldehyde as both substrate and hydrogen source, in combination with water. This reaction proceeds under mild aqueous reaction conditions. Additionally the use of a secondary phase for catalyst retention and recycling has been investigated with promising results.
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http://dx.doi.org/10.1002/cssc.201600824 | DOI Listing |
J Org Chem
October 2024
State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China.
Various -1,2,4-trihydrobenzo[][1,2]azaphosphinine 3-oxides are synthesized highly stereoselectively from generated phosphenes and formaldimines under microwave irradiation. Aryl(diazo)methyl(diaryl)phosphine oxides first undergo the Wolff rearrangement to generate phosphenes. Imines, generated from 1,3,5-triazinanes or paraformaldehyde and primary amines, nucleophilically attack the phosphenes followed by a tandem stereoelectronic effect-controlled intramolecular nucleophilic addition and aromatization to give final -1,2,4-trihydrobenzo[][1,2]azaphosphinine 3-oxides, exhibiting completely different annuloselectivity from linear nonformaldimines.
View Article and Find Full Text PDFPharmacol Res
November 2024
Neuroscience Research Institute, Gachon University, Incheon 21565, Republic of Korea; Department of Pharmacology, College of Medicine, Gachon University, Incheon 21999, Republic of Korea; Department of Health Science and Technology, Gachon Advanced Institute for Health Sciences & Technology, Gachon University, Incheon 21999, Republic of Korea. Electronic address:
Chem Sci
July 2024
Los Alamos National Laboratory Los Alamos New Mexico 87545 USA
A geometrically flexible bifunctional (bis)aminophosphine ligand was synthesized in a three-component, one-pot Kabachnik-Fields reaction using butylphosphine, paraformaldehyde, and 3,5-dimethyl aniline. The product, bis((3,5-dimethylphenyl)aminomethyl) butylphosphine (BiAMP ), containing two secondary amines and a tertiary phosphine, was isolated in good yields. Deprotonation of both N-H groups with (trimethylsilyl)methylpotassium (K-CHSiMe), followed by salt metathesis with LaI, YI, and LuI generated the corresponding MI(BiAMP )(thf) complexes (M = Y (1), La (2), and Lu (3)) in good yields.
View Article and Find Full Text PDFInt J Mol Sci
June 2024
Research Unit of Multimodal Cross Scale Neural Signal Detection and Imaging, HUST-Suzhou Institute for Brainsmatics, JITRI, Chinese Academy of Medical Sciences, Suzhou 215125, China.
Paraformaldehyde (PFA) fixation is the preferred method for preserving tissue architecture for anatomical and pathological observations. Meanwhile, PFA reacts with the amine groups of biomolecules to form chemical cross-linking, which preserves RNA within the tissue. This has great prospects for RNA sequencing to characterize the molecular underpinnings after anatomical and pathological observations.
View Article and Find Full Text PDFChem
February 2023
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
Various small molecules have been used as functional probes for tissue imaging in medical diagnosis and pharmaceutical drugs for disease treatment. The spatial distribution, target selectivity, and diffusion/excretion kinetics of small molecules in structurally complicated specimens are critical for function. However, robust methods for precisely evaluating these parameters in the brain have been limited.
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