This study described palladium-catalyzed chemoselective direct α-arylation of carbonyl compounds with chloroaryl triflates in the Ar-Cl bond. The Pd/SelectPhos system showed excellent chemoselectivity toward the Ar-Cl bond in the presence of the Ar-OTf bond with a broad substrate scope and excellent product yields. The electronic and steric hindrance offered by the -PR group of the ligand with the C2-alkyl group was found to be the key factor affecting the reactivity and chemoselectivity of the α-arylation reaction. The chemodivergent approach was also successfully employed in the synthesis of flurbiprofen and its derivatives (, -OMe and -F).
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http://dx.doi.org/10.1039/d1sc06701j | DOI Listing |
Org Lett
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Chemical Biology Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, People's Republic of China.
We present a versatile palladium-catalyzed glycosylation platform that enables facile access to structurally diverse N-O-linked glycosides with constantly excellent regio- and stereoselectivities. Importantly, this approach offers a broad substrate scope, low catalyst loadings, and outstanding chemoselectivity, allowing for the selective reaction of oximes/hydroximic acids over hydroxyl groups that would otherwise pose challenges in conventional glycosylation methods. The synthetic utility of this method is further exemplified through a range of synthetic transformations and late-stage modification of bioactive molecules.
View Article and Find Full Text PDFJ Org Chem
January 2025
State Key Laboratory of Macromolecular Drugs and Large-Scale Manufacturing, School of Pharmaceutical Sciences, Wenzhou Medical University, Wenzhou 325035, P. R. China.
The Pd-catalyzed multicomponent tandem reaction of β-ketonitriles, arylboronic acids and DMSO was efficiently developed, enabling access to a variety of poly substituted pyridines. The protocol shows excellent chemoselectivity, generating nicotinonitriles or symmetrical tetrasubstituted pyridines under different conditions by tandem cyclization of enaminone intermediates with β-ketonitriles or enolates, respectively, and does not require extra ammonias. This method boasts notable advantages, such as the use of commercially available or easily prepared substrates, simple conditions, a broad substrate scope, and good functional group tolerance.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, Indian Institute of Science Education and Research (IISER)-Pune, Dr. Homi Bhabha Road, Pashan, Pune, Maharashtra 411008, India.
A Pd (II)-catalyzed direct C3-(sp)-H alkenylation of heteroarenes using benzothiazole as a directing group was successfully achieved. A wide range of 2--alkylpyrroles undergo an oxidative coupling with a variety of acrylates to furnish highly regio- and chemoselective E-alkenylation products at the C3 position. An important intermediate complex has been isolated and characterized so as to have an insight into the mechanism.
View Article and Find Full Text PDFMolecules
November 2024
Department of General and Inorganic Chemistry, University of Pécs, Ifjúság u. 6., H-7624 Pécs, Hungary.
Palladium-catalyzed carbonylation reactions of -phenylene dihalides were studied using aminoethanols as heterobifunctional ,-nucleophiles. The activity of aryl-iodide and -bromide as well as the chemoselective transformation of amine and hydroxyl functionalities were studied systematically under carbonylation conditions. Aminocarbonylation can be selectively realized under optimized conditions, enabling the formation of amide alcohols, and the challenging alkoxycarbonylation can also be proved feasible, enabling amide-ester production.
View Article and Find Full Text PDFOrg Lett
December 2024
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, People's Republic of China.
A structure-dependent, palladium-catalyzed switchable alder-ene/[2π + 2σ] cycloaddition of VBCBs with α-ketoesters has been reported. A variety of cyclobutenes and 2-oxabicyclo[2.1.
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