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A readily available cyclic carbamate 1 functions as a general precursor to a range of functionalized piperidine products via a new Pd-catalyzed annulation strategy. An asymmetric catalytic variant provides a rapid and efficient means to access these heterocycles with high to excellent levels of enantiocontrol. Finally, these richly functionalized compounds are amenable to further chemoselective elaboration.
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http://dx.doi.org/10.1002/chem.201602586 | DOI Listing |
ChemSusChem
September 2025
Leibniz Institute for Catalysis e.V., Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
The palladium-catalyzed Suzuki-Miyaura cross coupling reaction to forge carbon-carbon bonds fundamentally changes the practice of organic synthesis. Herein an isolated palladium catalyst supported on polymeric carbon nitride (Pd/PCN) for efficient cross coupling of bromobenzene and phenylboronic acid at room temperature is reported. It is demonstrated that the Pd/PCN catalyst with a 2 wt% Pd loading achieves the highest mole-specific activity.
View Article and Find Full Text PDFOrg Lett
September 2025
Department of Medicinal Chemistry, National Institute of Pharmaceutical Education and Research (NIPER), Ahmedabad, Gujarat 382355, India.
Herein, we report an easily tunable and regioselective Pd-catalyzed allene-alkyne coupling protocol for the stereodivergent synthesis of - and -1,3-enynes using purine allenamine by a simple switch of ligands P(-tolyl)Ph and Boc-Phe-OH. For the first time, we have explored mono--protected amino acids (MPAAs) as ligands in allene-alkyne coupling to furnish -1,3-enynes selectively. This protocol streamlined the access to chiral 1,3-enynes and addressed the long-standing stereoselectivity challenges associated with 1,3-enynes from allene-alkyne coupling.
View Article and Find Full Text PDFOrg Biomol Chem
September 2025
Key Laboratory of Asymmetric Synthesis and Chirotechnology of Si-chuan Province, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China.
Based on a patented new concept of general chiral catalysis, a series of new chiral ligands integrating both a MacMillan imidazolinone organocatalyst and a chiral N,P-ligand scaffold has been designed and concisely prepared from commercially available chiral α-amino acids and 2-diphenylphosphino-benzaldehyde. These chiral ligands have shown good to excellent enantioselectivities (up to 97% ee) with satisfactory yields (up to 95%) in enantioselective Pd-catalyzed allylations with 1,3-dicarbonyls and amines.
View Article and Find Full Text PDFOrg Lett
September 2025
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, China.
A diastereoselective Pd-catalyzed allylic C-F bond functionalization of pentafluoroethyl alkenes is described. Heteroatom nucleophiles including amines, alcohols, and thiols can be employed to construct new C-N, C-O, or C-S bonds with concomitant cleavage of an allylic C-F bond. Both 1,1- and 1,2-disubstituted pentafluoroalkenes can be utilized to synthesize novel tetra- and trisubstituted alkenes containing an sp-carbon connected to both F and CF in good to excellent diastereoselectivities.
View Article and Find Full Text PDFJ Org Chem
August 2025
College of Chemistry, Chemical Engineering and Resource Utilization, Northeast Forestry University, Harbin 150040, P. R. China.
Using 4-bromoindole-3-carboxylic acid derivatives (amides or esters) as substrates, this paper successfully developed a trace water-promoted, palladium-catalyzed "one-pot" reaction strategy for synthesizing 4-amino/alkoxyindole-3-carboxylic acid products. With PdCl (5 mol %) as the precatalyst, Xantphos as the ligand, and cesium pivalate as the additive, this synthetic method innovatively integrates nucleophilic substitution of amides/esters with Pd-catalyzed C-N or C-O cross-coupling into a single reaction system, achieving efficient synergy of multistep transformations. This approach facilitates a modular and rapid assembly of multisubstituted indole-3-carboxylic acids, exhibiting broad functional group compatibility while maintaining good reaction yields.
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