While chemoselectivities in Pd -catalyzed coupling reactions are frequently non-intuitive and a result of a complex interplay of ligand/catalyst, substrate, and reaction conditions, we herein report a general method based on Pd that allows for an a priori predictable chemoselective Csp2 -Csp2 coupling at C-Br in preference to C-OTf and C-Cl bonds, regardless of the electronic or steric bias of the substrate. The C-C bond formations are extremely rapid (<5 min at RT) and are catalyzed by an air- and moisture-stable Pd dimer under open-flask conditions.
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http://dx.doi.org/10.1002/anie.201609635 | DOI Listing |
J Am Chem Soc
January 2025
Laboratory of Synthesis and Natural Products (LSPN), Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, CH-1015 Lausanne, Switzerland.
In the dyotropic rearrangement of molecules with semiflexible structures, characterized by a freely rotating static C-C bond, the formation of a mixture of products is common due to the coexistence of several energetically comparable conformers. Herein, we report that it is possible to modulate the shifting groups by adjusting the metal's coordination sphere in Pd-based dyotropic rearrangement. In the presence of a catalytic amount of Pd(II) salt, the reaction of γ-hydroxyalkenes or γ,δ-dihydroxyalkenes with Selectfluor affords fluorinated tetrahydropyranols or 6,8-dioxabicyclo[3.
View Article and Find Full Text PDFNat Commun
July 2024
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, China.
Cleavage of carbon-carbon bonds remains a challenging task in organic synthesis. Traditional methods for splitting C=C bonds into two halves typically involve non-redox (metathesis) or oxidative (ozonolysis) mechanisms, limiting their synthetic potential. Disproportionative deconstruction of alkenes, which yields one reduced and one oxidized fragment, remains an unexplored area.
View Article and Find Full Text PDFMolecules
April 2024
Dipartimento di Scienze Chimiche, Fisiche, Matematiche e Naturali, Università degli Studi di Sassari, Via Vienna 2, 07100 Sassari, Italy.
Aryl and heteroaryl iodides have been efficiently converted into the corresponding thioacetates in cyclopentyl methyl ether (CPME), a green solvent, under Cu catalysis. The chemoselectivity of the reaction is mainly controlled by electronic factors, enabling the conversion of both electron-rich and electron-deficient substrates into the corresponding thioacetates in good to excellent yields. The products can be easily deprotected to the corresponding thiolates to carry out additional synthetic transformations in situ.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2023
EaStCHEM, School of Chemistry, University of St Andrews, Purdie Building, North Haugh, St Andrews, KY16 9ST, UK.
We report the development of a C(sp )-C(sp ) coupling reaction using styrene boronic acids and redox-active esters under photoredox catalysis. The reaction proceeds through an unusual polarity-mismatched radical addition mechanism that is orthogonal to established processes. Synergistic activation of the radical precursor and organoboron are critical mechanistic events.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2023
Dipartimento di Farmacia-, Scienze del Farmaco, Università di Bari "Aldo Moro", Consorzio C.I.N.M.P.I.S., Via E. Orabona 4, 70125, Bari, Italy.
Advancing the development of perfecting the use of polar organometallics in bio-inspired solvents, we report on the effective generation in batch of organosodium compounds, by the oxidative addition of a C-Cl bond to sodium, a halogen/sodium exchange, or by direct sodiation, when using sodium bricks or neopentylsodium in hexane as sodium sources. C(sp )-, C(sp )-, and C(sp)-hybridized alkyl and (hetero)aryl sodiated species have been chemoselectively trapped (in competition with protonolysis), with a variety of electrophiles when working "on water", or in biodegradable choline chloride/urea or L-proline/glycerol eutectic mixtures, under hydrous conditions and at room temperature. Additional benefits include a very short reaction time (20 s), a wide substrate scope, and good to excellent yields (up to 98 %) of the desired adducts.
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