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Cross-coupling azide and isocyanide have recently gained recognition as ideal methods for efficiently synthesizing asymmetric carbodiimides. This reaction exhibits high reaction rates, efficiency, and favorable atom/step/redox economy. It enables the nitrene-transfer process, facilitating the formation of C-N bonds and providing a direct and cost-effective synthetic strategy for generating diverse carbodiimides. These carbodiimides are highly reactive compounds that can undergo transformations into various functional groups and organic compounds, including heterocycles. Developing one-pot and tandem processes in this field has significantly contributed to advancements in organic chemistry. Moreover, the demonstrated utility of these architectural motifs extends to areas such as chemical biology and medicinal chemistry, further highlighting their potential in various scientific applications.
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http://dx.doi.org/10.1016/j.isci.2024.109311 | DOI Listing |
J Org Chem
September 2025
Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation, College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, China.
The generation of α-imino metal carbenes from readily available alkynes via nitrene transfer has emerged as an important advancement in carbene chemistry, but current methodologies remain constrained to noble-metal catalysts. Additionally, the dearomatization involving α-imino metal carbenes has not been unexplored. In this study, we disclose a copper-catalyzed dearomatization reaction of azides with ynamide-phenol derivatives via α-imino copper carbenes.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Chemistry, Indian Institute of Science Education and Research Pune, Dr. Homi Bhabha Road, Pashan, Pune 411008, Maharashtra, India.
An iron-based metalloradical activation concept is developed for an intramolecular molecular rearrangement via ester migration and an allylic C(sp)-H amination using tetrazole as a nitrene precursor. It has been shown that an appropriate choice of catalyst can switch the chemoselectivity of a particular substrate from molecular rearrangement toward allylic C(sp)-H amination. The scope of the reactions has been demonstrated by the use of a wide number of tetrazoles and aryl azides.
View Article and Find Full Text PDFOrg Biomol Chem
June 2025
Innovation Center for Chemical Sciences, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou Industrial Park, Suzhou, Jiangsu 215123, China.
Computational studies were carried out to shed light on the mechanism of photocatalytic nitrene transfer reactions of benzoyl azide in the presence of phosphoric acid. The formed H-bonding complex of benzoyl azide with HPO would readily undergo single electron reduction with the excited *Ru(II) photocatalyst, followed by sequential proton transfer and N dissociation to give a key N-centered radical. The energy transfer mechanistic pathway leading to a protonated nitrenium species, however, might not be feasible.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
May 2025
Institute of Physics, Czech Academy of Sciences, Cukrovarnická 10, 16200, Prague 6, Czech Republic.
Nitrenes are known as key intermediates in various chemical reactions. Nitrene transfer reactions are particularly effective for synthesizing nitrogen-containing compounds, where metal catalysts play a crucial role in controlling nitrene reactivity and selectivity. In this study, we demonstrate the formation of a stable surface-supported dinitrene on Au(111) through UV irradiation of its diazide precursor, characterized by scanning probe techniques.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
School of Chemistry and Chemical Engineering, Frontier Scientific Center of Transformative Molecules, Shanghai Key Laboratory of Chiral Drugs and Engineering, Shanghai Jiao Tong University, Shanghai, Minhang 200240, China.
An asymmetric intramolecular spiro-amination to high steric hindering -C-H bond of 1,3-dicarbonyl via nitrene transfer using inactive aryl azides has been carried out by developing a novel Cp*Ir(III)-SPDO (spiro-pyrrolidine oxazoline) catalyst, thereby enabling the first successful construction of structurally rigid spiro-quaternary indolinone cores with moderate to high yields and excellent enantioselectivities. DFT computations support the presence of double bridging H-F bonds between [SbF] and both the ligand and substrate, which favors the plane-differentiation of the enol π-bond for nitrenoid attacking. These findings open up numerous opportunities for the development of new asymmetric nitrene transfer systems.
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