Allylic amination reactions enable the conversion of alkene feedstocks into value-added products with significant synthetic versatility. Here we describe a method for allylic amination involving photoredox activation and Cu(II)-mediated radical-polar crossover. A range of structurally varied allylic amines can be accessed using this strategy. The regioselectivity of this process is complementary to those of conventional methods for allylic amination.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10351055 | PMC |
http://dx.doi.org/10.1021/acs.orglett.3c01774 | DOI Listing |
Molecules
January 2025
Université de Reims Champagne-Ardenne, CNRS, ICMR, 51097 Reims, France.
A straightforward synthetic route towards DAB-1 scaffolded dimeric iminosugars is described here, starting from readily available bis-glycosylamines. The method allows the integration of a variety of linkages (aryl, alkyl, polyethyleneglycol chains) between both iminosugars through the choice of the bis-amine used in the first step. Moreover, an additional substituent (allyl, ethynyl) may be inserted into the structure via nucleophilic addition of an organometallic reagent to the starting bis-glycosylamine.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Medicinal and Process Chemistry Division, CSIR-Central Drug Research Institute, Lucknow 226031, India.
The construction of complex molecules under metal-free conditions multiple bond-forming steps in a cascade manner is highly desirable. Herein, we have developed an HFIP-alone promoted aminomethylation and intramolecular cyclization of allenamides, providing biologically relevant tetrahydro-β-carboline derivatives embedded with an allylic amine functionality. The metal-free protocol provided the desired tetrahydro-β-carboline derivatives under mild conditions.
View Article and Find Full Text PDFOrg 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
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur, 741246, West Bengal, India.
Chiral allylamines 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 allylamines. 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 PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!