A highly efficient formal allylation of dihydronaphthotriazoles with alkenes under rhodium(II) catalysis is reported. Various allyl dihydronaphthalene derivatives were furnished via rhodium(II) azavinyl carbenes with moderate to good yields and excellent chemoselectivity. When monosubstituted alkenes are used, cyclopropanation occurs and good to excellent enantioselectivities have been achieved. Particularly noteworthy is the allylic C(sp)-H activation instead of traditional C(sp)-H activation in the formal allylation process.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.0c04251 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Enantioselective Heck/Tsuji-Trost reaction of flexible vinylic halides with 1,3-dienes.
Nat Commun
January 2025
College of Chemistry and Life Science, Advanced Institute of Materials Science, Changchun University of Technology, Changchun, P. R. China.
The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress in relative rigid skeleton substrates, the implementation of asymmetric Heck/cross-coupling cascades of highly flexible haloalkene substrates remains a challenging and and long-standing goal. Here we report an efficient asymmetric domino Heck/Tsuji-Trost reaction of highly flexible vinylic halides with 1,3-dienes enabled by palladium catalysis.
View Article and Find Full Text PDFDirhodium-Palladium Dual-Catalyzed [1 + 1 + 3] Annulation to Heterocycles Using Primary Amines or HO as the Heteroatom Sources.
J 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 PDFA trimetallic bismuth(I)-based allyl cation.
Nat Chem
January 2025
Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany.
The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based π-allyl cation.
View Article and Find Full Text PDFSynthesis of Carboxylic Acids Containing α-All-Carbon Quaternary Centers from Diazo Compounds and Trialkylboranes.
J Org Chem
January 2025
Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
The construction of C-C bonds to form all-carbon quaternary centers remains a significant challenge in synthetic chemistry. Herein, we report a tandem process involving a 1,2-migration of a tetra-coordinated boron intermediate followed by a Claisen rearrangement of the boron enolate, achieved through a reaction between allyl diazoacetates and trialkylboranes. The transformation forms two C-C bonds at the carbenic position of diazo substrate in a single-step operation under neutral conditions.
View Article and Find Full Text PDFIn-Cage Recombination Facilitates the Enantioselective Organocatalytic [1,2]-Rearrangement of Allylic Ammonium Ylides.
J Am Chem Soc
January 2025
EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St. Andrews, KY16 9ST, U.K.
The [1,2]-rearrangement of allylic ammonium ylides is traditionally observed as a competitive minor pathway alongside the thermally allowed [2,3]-sigmatropic rearrangement. Concerted [1,2]-rearrangements are formally forbidden, with these processes believed to proceed through homolytic C-N bond fission of the ylide, followed by radical-radical recombination. The challenges associated with developing a catalytic enantioselective [1,2]-rearrangement of allylic ammonium ylides therefore lie in biasing the reaction pathway to favor the [1,2]-reaction product, alongside controlling a stereoselective radical-radical recombination event.
View Article and Find Full Text PDFWant 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!