skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


  • NSF Public Access
  • Search Results
  • Synthesis of Symmetric and Unsymmetric Secondary Amines from the Ligand-Promoted Ruthenium-Catalyzed Deaminative Coupling Reaction of Primary Amines
Title: Synthesis of Symmetric and Unsymmetric Secondary Amines from the Ligand-Promoted Ruthenium-Catalyzed Deaminative Coupling Reaction of Primary Amines
Award ID(s):
1664652
PAR ID:
10097841
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
The Journal of Organic Chemistry
Volume:
83
Issue:
9
ISSN:
0022-3263
Page Range / eLocation ID:
4932 to 4947
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; (, SynOpen)
    null (Ed.)
    Abstract Amines such as 1,2,3,4-tetrahydroisoquinoline undergo redox­-neutral annulations with ortho-(nitromethyl)benzaldehyde. Benzoic­ acid acts as a promoter in these reactions, which involve concurrent amine α-C–H bond and N–H bond functionalization. Subsequent removal of the nitro group provides access to tetrahydroprotoberberines not accessible via typical redox-annulations. Also reported are decarboxylative annulations of ortho-(nitromethyl)benzaldehyde with proline and pipecolic acid. 
    more » « less
  2. ; ; ; (, Chirality)
    Isatins are extensively researched compounds with diverse applications, particularly as synthetic precursors in pharmaceutical developments. However, their use as optical probes for enantioselective sensing of chiral amines has not been explored to date. Herein, we present a novel chiroptical assay with an optimized isatin that generates strong, red‐shifted circular dichroism (CD) signals at approximately 380 nm upon ketimine formation with chiral amines. The intensity of the induced CD signal increases linearly with the enantiomeric excess of the analyte and thus allows quantitative chirality analysis. The general usefulness of this approach is demonstrated with a broad range of aliphatic and aromatic chiral amines, and by accurate determination of the enantiomeric composition of 10 samples. 
    more » « less
  3. ; ; ; (, Organic & biomolecular chemistry)
    The development of new transamidation reactions for the synthesis of amides is an important and active area of research due to the central role of amide linkage in various fields of chemistry. Herein, we report a new method for transamidation of N-acyl-glutarimides with amines under mild, metal-free conditions that relies on amide bond twist to weaken amidic resonance. A wide range of amines and functional groups, including electrophilic substituents that would be problematic in metal-catalyzed protocols, are tolerated under the reaction conditions. Mechanistic experiments implicate the amide bond twist, thermodynamic stability of the tetrahedral intermediate and leaving group ability of glutarimide as factors controlling the reactivity of this process. The method further establishes the synthetic utility of N-acyl-glutarimides as bench-stable, twist-perpendicular, amide-based reagents in acyl-transfer reactions by a metal-free pathway. The origin of reactivity of N-acyl-glutarimides in metal-free and metal-catalyzed processes is discussed and compared. 
    more » « less
  4. ; ; ; ; ; (, Organic Chemistry Frontiers)
    Enantioenriched azaarylmethyl amine derivatives are useful building blocks in synthetic and medicinal chemistry. To access these valuable motifs, an enantioselective palladium-catalyzed benzylation of azaarylmethyl amine pronucleophiles is introduced. Of note, this is a rare application of asymmetric (2-naphthyl)methylation of pro-nucleophiles with high p K a values (p K a ≈ 34 in DMSO). Control experiments support the notion that the coordination of Li + to the azaaryl nitrogen plays a critical role in the substitution process. With this procedure, enantioenriched (2-naphthyl)methylene azaarylmethyl amines with a variety of azaaryl groups (pyridyl, pyrazine, quinoxaline and isoquinoline) and cyclic and acyclic amines are readily obtained with good yields and enantioselectivities up to 99%. 
    more » « less
  5. ; ; ; ; ; ; (, Tetrahedron)
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email