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Palladium catalyzed allylic C-H functionalization was performed using exocyclic alkene substrates. Multi-component synthesis of stereodefined homoallylic alcohols could be performed using a reaction sequence involving allylic C-H borylation and allylation of aldehydes.
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http://dx.doi.org/10.1039/c4cc04151h | DOI Listing |
Nat Commun
September 2025
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
Arenes bearing silyl and boryl, or germyl and boryl groups, represent a significant class of bifunctional molecules that have garnered considerable attention in organic synthesis due to their unique reactivity and versatility in undergoing diverse chemical transformations. Despite their importance, the synthesis of these mixed-metalloid compounds, particularly those with ortho-substituted aromatic frameworks, often involves complex, multi-step procedures. Herein, we present a highly efficient, single-step method for synthesizing ortho-boronated arylhydrosilanes and arylgermanes via catalytic C-H borylation reaction.
View Article and Find Full Text PDFDalton Trans
August 2025
EaStCHEM School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, UK.
C-H zincation is an efficient route to useful organozinc compounds. To date, most approaches effect aryl C-H zincation with selectivity controlled by substrate p. Herein, we report a heteroaryl C-H zincation method that uses an easy to access (β-diketiminate)Zn-Me complex and [(RN)H][Anion] and proceeds under electronic control.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, China.
The enantioselective functionalization of inert C(sp)-H bonds is one of the most significant challenges in modern synthetic chemistry, especially when it is applied to structurally complex compounds. To achieve success, we require a comprehensive understanding of the mechanisms involved in controlling enantioselectivity, but such knowledge is currently limited. Herein, we systematically investigated the catalysis of chiral iridium complexes for the C(sp)-H borylation of tetrahydroisoquinoline (THIQ) using DFT calculations with a careful conformational search of transition states.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Chemistry and Nanoscience, Ewha Womans University, Seoul 03760, Korea.
The C-H amination of arenes offers a path for the synthesis of important arylamines that precludes the need for the prior functionalization of arene substrates, for example through halogenations or metalations. Most often, the direct C-H amination of arenes was achieved using transition metal or photoredox catalysis, through mechanisms ranging from electrophilic substitution to radical additions or nitrene insertions. Here, we report that azidium ions enabled the telescoped C-H amination of unactivated arenes and heteroarenes through a cycloaddition and C-N/N-N bond cleavage sequence.
View Article and Find Full Text PDFOrg Lett
July 2025
State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China.
A novel one-pot, two-step strategy for late-stage aryl -C-H bond carboxylation of anilines with CO has been developed. This methodology combines BBr-mediated aryl -C-H bond borylation and ZnEt-promoted C-B bond carboxylation, enabling the efficient synthesis of diverse -aminobenzoic acid derivatives. The protocol eliminates the requirement for precious metal catalysts and bulky non-labile directing groups, potentially serving as an efficient approach for installing a carboxylic acid group in functional molecules.
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