Dehydrogenative cross-coupling reaction of primary anilines, secondary anilines, carboxamides, and sulfonamides with 1,3-diarylpropenes to form a series of allylic amines promoted by DDQ have been realized. Both monoallylation and diallylation products can be selectively synthesized when primary anilines are used as the starting materials. The method may provide a wide scope of allylamines in scientific research including biologically active compound library construction.
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http://dx.doi.org/10.1039/c2ob06826e | DOI Listing |
Org Lett
January 2025
China Guangxi Key Laboratory of Pharmaceutical Precision Detection and Screening, Guangxi Key Laboratory of Bioactive Molecules Research and Evaluation, and Key Laboratory of Micro-Nanoscale Bioanalysis and Drug Screening of Guangxi Education Department, Pharmaceutical College, Guangxi Medical University, Nanning 530021, China.
Herein, a one-pot domino catalyzed three-component process is described, which is initiated by a palladium/zinc cooperatively catalyzed cycloaddition between trimethylenemethane (TMM) and unactivated alkyl/aryl imines, followed by one-pot isomerization and Zn(OTf)-catalyzed DDQ oxidation, furnishing valuable substituted pyrroles. We disclose that the palladium/zinc cooperative catalysis affords a dual-Zn(OTf)-stabilized azapalladacycle, wherein the Pd-N bond is polarized by Zn(OTf), facilitating a unique outer-sphere allylic amination. Moreover, subsequent DDQ dehydrogenation can be feasibly promoted by zinc catalysis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
IISER Kolkata: Indian Institute of Science Education and Research Kolkata, Department of Chemical Sciences, Mohanpur, 741246, Nadia, INDIA.
Chiral allyl amines are important structural components in natural products, pharmaceuticals, and chiral catalysts. Herein, we report a cobalt-catalyzed enantioselective reductive coupling of imines with internal alkynes to synthesize chiral allyl amines. The reaction is catalyzed by a cobalt complex derived from commercially available bisphosphine ligand utilizing zinc as the electron donor.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
The ever-increasing demand in chemical biology and medicinal research requires the development of new synthetic methods for the rapid construction of libraries of heterocycles from simple raw materials. In this context, the utilization of primary amines or HO as the simple - or -sources in the assembly of a heterocyclic ring skeleton is highly desirable from the viewpoint of atom- and step-economy. Herein, we describe a highly efficient three-component reaction of diazo, allylic diacetates, and commercially available anilines (or HO) to access structurally diverse pyrrolidine and tetrahydrofuran derivatives.
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, Wayne State University, Detroit, Michigan 48202, United States.
The utilization of β-fluoroamines as pharmaceutical components for drug development has attracted a considerable amount of interest. However, direct access to tertiary β-fluoroamines is challenging. We herein report the rhodium-catalyzed asymmetric amination of tertiary allylic trichloroacetimidates with anilines and cyclic aliphatic amines to access tertiary β-fluoroamines, where the α-carbon atom is bonded to four different substituents, in good yield with high levels of enantioselectivity.
View Article and Find Full Text PDFJ Org Chem
January 2025
Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan.
Using amines in catalytic transfer hydrogenation (TH) is challenging, despite their potential availability as a hydrogen source. Here, we describe a photoredox/nickel-catalyzed TH of alkyne through an intermediary aminoalkyl Ni species. This reaction successfully provided functionalized ()-alkenes, such as (homo)allyl ethers, alcohols, and amides (/ = up to >99:1), and the reaction thus bypasses a limitation of substrate scope in TH using amine and a Lindlar catalyst.
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