A new class of bioorthogonal reagents based on the cyclopentadiene scaffold is described. The diene 6,7,8,9-tetrachloro-1,4-dioxospiro[4,4]nona-6,8-diene (a tetrachlorocyclopentadiene ketal, TCK) is ambiphilic and self-orthogonal with remarkable stability. The diene reacts rapidly with a trans-cyclooctene and an endo-bicyclononyne, but slowly with dibenzoazacyclooctyne (DIBAC), allowing for tandem labeling studies with mutually orthogonal azides that react rapidly with DIBAC. TCK analogues are synthesized in three steps from inexpensive, commercially available starting materials.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6314806 | PMC |
| http://dx.doi.org/10.1021/jacs.8b02978 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
A catalytic collaboration: pairing transition metals and Lewis acids for applications in organic synthesis.
Dalton Trans
August 2024
Department of Chemistry, Western University, 1151 Richmond Street, London, ON, N8K 3G6, Canada.
The use of metal catalysts to accelerate an organic transformation has proven indispensable for access to structural motifs having applications across medicinal, polymer, materials chemistry, and more. Most catalytic approaches have cast transition metals in the "leading role"; these players mediate important reactions such as C-C cross coupling and the hydrogenation of unsaturated bonds. These catalysts may require collaboration, featuring Lewis acidic or basic additives to promote a desired reaction outcome.
View Article and Find Full Text PDFPhotogeneration of α-Bimetalloid Radicals via Selective Activation of Multifunctional C1 Units.
J Am Chem Soc
June 2024
Department of Biomolecular Systems, Max-Planck-Institute of Colloids and Interfaces, Potsdam 14476, Germany.
Light-driven strategies that enable the chemoselective activation of a specific bond in multifunctional systems are comparatively underexplored in comparison to transition-metal-based technologies, yet desirable when considering the controlled exploration of chemical space. With the current drive to discover next-generation therapeutics, reaction design that enables the strategic incorporation of an sp carbon center, containing multiple synthetic handles for the subsequent exploration of chemical space would be highly enabling. Here, we describe the photoactivation of ambiphilic C1 units to generate α-bimetalloid radicals using only a Lewis base and light source to directly activate the C-I bond.
View Article and Find Full Text PDFRegioselective Palladium-Catalyzed Chain-Growth Allylic Amination Polymerization of Vinyl Aziridines.
J Am Chem Soc
June 2024
Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599, United States.
Organometallic-mediated chain growth polymerization of readily accessible chemical building blocks is responsible for important commercial and technological advances in polymer science, but the incorporation of heteroatoms into the polymer backbone through these mechanisms remains a challenge. Transition metal π-allyl complexes are well-developed organometallic intermediates for carbon-heteroatom bond formation in small-molecule catalysis yet remain underexplored in polymer science. Here, we developed a regioselective palladium-phosphoramidite-catalyzed chain-growth allylic amination polymerization of vinyl aziridines for the synthesis of novel nitrogen-rich polymers via ambiphilic π-allyl complexes.
View Article and Find Full Text PDFπ-Electron Fluctuation-Induced P /C Ambiphilic Interaction for Intramolecular C -H Bond Activation.
Chemistry
February 2024
College of Chemistry, Green Catalysis Center, International Phosphorus Laboratory, Zhengzhou University, 450001, Zhengzhou, China.
Herein, we describe how computational mechanistic understanding has led directly to the discovery of new 2H-phosphindole for C-C bond activation and dearomatization reaction. We uncover an unexpected intramolecular C-H bond activation with a 2H-phosphindole derivative. This new intriguing experimental observation and further theoretical studies led to an extension of the reaction mechanism with 2H-phosphindole.
View Article and Find Full Text PDFConvergent Deboronative and Decarboxylative Phosphonylation Enabled by the Phosphite Radical Trap "BecaP".
J Am Chem Soc
August 2023
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, U.K.
Carbon-phosphorus bond formation is significant in synthetic chemistry because phosphorus-containing compounds offer numerous indispensable biochemical roles. While there is a plethora of methods to access organophosphorus compounds, phosphonylations of readily accessible alkyl radicals to form aliphatic phosphonates are rare and not commonly used in synthesis. Herein, we introduce a novel phosphorus radical trap "BecaP" that enables facile and efficient phosphonylation of alkyl radicals under visible light photocatalytic conditions.
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!