An atom-economical methodology for the synthesis of sterically hindered tertiary amines was developed, which is based on complementary Rh- and Ru-catalyzed direct reductive amination of ketones with primary and secondary amines using carbon monoxide as a deoxygenating agent.

Download full-text PDF

Source
http://dx.doi.org/10.1039/c5cc08577bDOI Listing

Publication Analysis

Top Keywords

synthesis sterically
8
sterically hindered
8
direct reductive
8
reductive amination
8
amination ketones
8
hindered amines
4
amines direct
4
ketones atom-economical
4
atom-economical methodology
4
methodology synthesis
4

Similar Publications

Synthesis and Reactivity of a Bipyridyl Tantalum Complex.

Inorg Chem

January 2025

Testing and Analysis Center, Hebei Normal University, Shijiazhuang 050024, China.

The bipyridyl tantalum complex (2,6-PrCHO)Ta(bipy) () is synthesized by the reaction of (2,6-PrCHO)TaCl () and 2,2'-bipyridine in the presence of excess potassium graphite (KC). Complex coordinates readily with pyridine and 4-(dimethylamino)pyridine (dmap) to form Lewis base adducts (2,6-PrCHO)Ta(bipy)(L) (L = py (), dmap ()), and it exhibits rich redox reactivity toward small molecules: (a) single electron transfer (SET) occurs upon exposure of to phenyl sulfide or selenide dimer, giving the open-shell, bipy-centered radical complexes (2,6-PrCHO)Ta(bipy)(PhE) (E = S (), Se ()). (b) Regioselective C-C σ-bond formation via radical coupling is observed in the SET reaction of and aldehydes, ketones, or imines to furnish insertion products -, namely, sterically more crowded benzophenone, acetophenone, 2,6-dichlorobenzaldehyde, and benzophenone imine couple with C6 or C6' of bipy in , respectively, whereas sterically less hindered benzaldehyde, cyclohexanone, and benzylideneaniline couple with C2 or C2' of bipy, respectively.

View Article and Find Full Text PDF

Synthesis of anisotropic silica nanoparticles by organic amine with diverse structures.

Nanotechnology

January 2025

School of Chemical Science and Engineering, Tongji University, Shanghai, People's Republic of China.

Herein, we synthesized anisotropic silica nanoparticles (AISNPs) with organic amines with different structures. Monoamines and diamines with distance between amine groups shorter than4 Å have been observed to facilitate the formation of isotropic silica nanoparticles (ISNPs). AISNPs were synthesized with diamines with distance between amine groups longer than4 Å and linear structures of triamines.

View Article and Find Full Text PDF

Water-soluble porphyrins have garnered significant attention due to their broad range of applications in biomedicine, catalysis, and material chemistry. In this work, water-soluble platinum(II) and palladium(II) complexes with porphyrins bearing ethyl phosphonate substituents, namely, Pt/Pd 10-(ethoxyhydroxyphosphoryl)-5,15-di(-carboxyphenyl)porphyrins (M3m, M = Pt(II), Pd(II)) and Pt/Pd 5,10-bis(ethoxyhydroxyphosphoryl)-10,20-diarylporphyrins (M1d-M3d; aryl = -tolyl (1), mesityl (2), -carboxyphenyl (3)), were synthesized by alkaline hydrolysis of the corresponding diethyl phosphonates M6m and M4d-M6d. NMR, UV-vis, and fluorescence spectroscopy revealed that the mono-phosphonates M3m tend to form aggregates in aqueous media, while the bis-phosphonates M3d exist predominantly as monomeric species across a wide range of concentrations (10-10 M), ionic strengths (0-0.

View Article and Find Full Text PDF

Interrupting Associative π-σ-π Isomerization Enables -Retentive Asymmetric Tsuji-Trost Reaction.

J Am Chem Soc

January 2025

New Cornerstone Science Laboratory, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.

The asymmetric Tsuji-Trost reaction has been extensively studied due to its importance in establishing stereogenic centers, often adjacent to an -olefin moiety in organic molecules. The generally preferential formation of chiral -olefin products is believed to result from the thermodynamically more stable -π-allylpalladium intermediate. The rapid associative π-σ-π isomerization makes it challenging to synthesize chiral -olefin products via the transient -π-allylpalladium intermediate.

View Article and Find Full Text PDF

Ring expansion metathesis polymerization (REMP) has emerged as a potent strategy for obtaining cyclic polymers over the past two decades. The scope of monomers, however, remains limited due to the poor functional group tolerance and stability of the catalyst, necessitating a rational catalyst design to address this constraint. Here, we present ruthenium complexes featuring tethered cyclic (alkyl)(amino)carbene ligands for REMP, aiming to deepen our understanding of the structure-property relationship in newly designed catalysts.

View Article and Find Full Text PDF

Want 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!