2-(2'-Pyridyl)-3,4,5,6-tetraphenylpyridine 2 (HL), a ligand with both N,N-bidentate and N,N,C-terdentate coordination potential, was prepared in excellent yield by the Diels-Alder [2+4] cycloaddition of 2-cyanopyridine and tetraphenylcyclopentadien-1-one. Monometallic Pd(II) and Rh(III) complexes were formed which exhibit both types of ligand coordination (trans-[RhCl2(L)(NCMe)] 3, cis-[RhCl(L)(NCMe)2]PF6, cis-[RhCl2(HL)2]PF6 6, [RhCl(L)(HL)]PF6 7, [Rh(L)2]PF6 8, [Pd(OAc)(L)] 9 and [Pd(eta3-methallyl)(HL)]PF6) 10. The molecular structures of the ligand and six complexes, including the chloro-bridged dimer [RhCl(L)(micro-Cl)]2 5, were obtained by single crystal X-ray diffraction.
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http://dx.doi.org/10.1039/b709818a | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Shandong University, Chemistry and Chemical Engineering, Shanda South Road 27, 250100, Jinan, CHINA.
Catalytic transformation of carbene species constitutes a fundamental part in organic synthesis, and the research in this direction has been dominated by transition metals while organic catalysts are difficult to mimic such transition-metal-like reactivity. It would significantly advance carbene chemistry if organic catalysts enable achieving classical metal-carbene approaches otherwise unrealizable reactions. Herein, we report that chalcogen bonding catalysis can solve reactivity problem to achieve an elusive Buchner ring expansion of aryl ketones appending a cyclopropene moiety as carbene precursor.
View Article and Find Full Text PDFAdv Mater
December 2024
Key Laboratory of Green Chemistry and Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China.
Chemistry
December 2024
Laboratorium für Organische Chemie (D-CHAB), ETH Zürich, Vladimir-Prelog-Weg 3, HCI, 8093, Zürich, Switzerland.
The power and ability of catalysis to build multiple C-C bonds in a single step has had a transformative impact on organic synthesis. While the reactivity of organohalides with metal catalysts is widely appreciated, the related and more intricate reactivity of acid chlorides is less so, despite their use as common reagents in synthesis. Here, we review the transformations of acid chlorides in combination with unsaturated C-C bonds catalyzed by palladium, rhodium, or iridium and provide an outlook for future research opportunities.
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
School of Science, Harbin Institute of Technology (Shenzhen), Shenzhen 518055, China.
Disulfide bonds are essential in protein folding, cellular redox balance, materials science, and drug development. Despite existing synthetic methods, the efficient and selective synthesis of unsymmetrical disulfides remains challenging. This review highlights innovative approaches in visible light photocatalysis, including decarboxylation, deoxydisulfidation of alcohols, and direct C-H disulfidation, showcasing broad substrate applicability and functional group tolerance under mild conditions.
View Article and Find Full Text PDFAcc Chem Res
October 2024
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
ConspectusAlkenes and alkynes are fundamental building blocks in organic synthesis due to their commercial availability, bench-stability, and easy preparation. Selective functionalization of alkenes and alkynes is a crucial step for the synthesis of value-added compounds. Precise control over these reactions allows efficient construction of complex molecules with new functionalities.
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