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A migratory insertion of carbenes into distal γ-C(sp)-H bonds of aliphatic amines has been successfully developed. The synergistic interplay among a palladium catalyst, picolinamide directing group, a carefully selected base additive, and an essential ligand proved crucial in achieving high yields. These findings hold significant value for advancing the exploration of regioselective carbene insertions into nonactivated C(sp)-H bonds.
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http://dx.doi.org/10.1021/acs.orglett.4c00038 | DOI Listing |
J Am Chem Soc
September 2025
State Key Laboratory of Antiviral Drugs, Tianjian Laboratory of Advanced Biomedical Sciences, Pingyuan Laboratory, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
The C-H functionalization represents a universal and important method for constructing new C-C bonds by carrying out reactions directly on inert C-H bonds. The major challenges are to control the site-selectivity and chemoselectivity because most complex organic compounds have many similar C-H bonds or different functional groups, such as a C═C bond or O-H bond. Here, we develop a versatile copper cluster (CuNC) with high stability and dynamic catalytic sites.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
Department of Chemistry, Indian Institute of Technology, Madras, Tamil Nadu, 600036, India.
A synthetic method has been developed for the diastereoselective domino synthesis of indolyl-pyrrolo[2,1-]isoindoles from phthalimide-derived -sulfonyl-1,2,3-triazoles and indoles. The reaction proceeds ring chain isomerization of triazoles to give α-imino diazo compounds. Then, denitrogenative generation of α-imino Rh(II) carbenes followed by intramolecular oxygen insertion and nucleophilic addition of indoles delivers the indolyl-pyrrolo[2,1-]isoindoles.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States.
Once physical organic curiosities, bicyclo[2.1.0]pentanes (colloquially termed housanes) are useful strain-release reagents and are unique structural motifs for medicinal chemistry campaigns because of their high Fsp content.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
Bicyclo[1.1.1]pentanes (BCPs) play crucial roles as saturated bioisosteric replacements of planar benzene rings.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Combustion Research Facility, Sandia National Laboratories, Livermore, California 94551, United States.
Sugars are produced by living organisms, and are required building blocks for life as we know it, which raises the foundational question of how sugars formed in a prebiotic environment. The abiotic formose reaction produces sugars from formaldehyde, but our understanding of its initiation step remains murky, with chemists invoking the concept of an "activated aldehyde" to seed this reaction. Singlet hydroxycarbenes, high-energy isomers of aldehydes, were recently reported to facilitate sugar formation under cold, nonaqueous conditions relevant to interstellar environments.
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