Cyclometalated ruthenium(II)-complex-catalyzed selective oxidative scission of olefins to carbonyls is described. A strong C-donor ligand, paired with a rigid backbone and redox activity of ruthenium, provided high catalytic activity and a long lifetime for olefin oxidation. The catalyst tolerates numerous functional groups and applies to challenging biomass-, natural-product-, sugar-, amino-acid-, and fatty-acid-derived substrates.
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http://dx.doi.org/10.1021/acs.orglett.4c03595 | DOI Listing |
J Am Chem Soc
December 2024
Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
Hydroalkylation of terminal alkynes is a powerful approach to the synthesis of disubstituted alkenes. However, its application is largely unexplored in the synthesis of α,β-unsaturated carbonyls, which are common among synthetic intermediates and biologically active molecules. The thermodynamically less stable -isomers of activated alkenes have been particularly challenging to access because of their propensity for isomerization and the paucity of reliable -selective hydroalkylation methods.
View Article and Find Full Text PDFACS Omega
December 2024
N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation.
The electrochemically induced reaction between alkenes, bearing an allylic hydrogen atom, and -hydroxyphthalimide was investigated. Cross-dehydrogenative C-O coupling with phthalimide--oxyl radical, derived from -hydroxyphthalimide, occurs instead of oxidation of the allylic site, with the formation of a carbonyl group or functionalization of the double C=C bond. The discovered transformation proceeds in an undivided electrochemical cell equipped with a carbon felt anode and a platinum cathode.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Frontiers Science Center for New Organic Matter, Tianjin 300071, China.
The development of effective synthetic methods to construct γ-lactams bearing a chiral α-quaternary carbon from relatively inert C(O)-H bonds with alkenes has been an elusive challenge. Herein, we used a naphthylamine-derived phosphine oxide ligating Ni and Al bimetallic catalyst to realize a carbonylative cyclization of formyl C-H bonds with alkenes, highly regio- and enantioselectively constructing γ-lactams bearing a chiral α-quaternary carbon in up to 99% yield and 98% ee. These γ-lactams proved to be versatile synthetic precursors for many biologically active molecules.
View Article and Find Full Text PDFChemistry
December 2024
Indian Institute of Technology Kanpur, Department of Chemistry, IIT, Kanpur, 208 016, Kanpur, INDIA.
Porous organic polymers (POPs) are novel emergent materials for heterogeneous organocatalysis owing to their remarkable physicochemical stabilities. Through a bottom-up approach entailing diligent design of twisted biaryl building blocks with in-built o-iodobenzoic acid (IA) moieties, a series of POP precatalysts, p-OMeIA-POP, DiMeIA-POP, and m-OMeIA-POP, were synthesized by employing Friedel-Crafts alkylation. These IA-POP precatalysts can undergo in situ oxidation in the presence of Oxone® to generate hypervalent iodine(V) species (λ5-iodanes), in particular, modified o-iodoxybenzoic acid, popularly termed IBX, which mediates diverse oxidative transformations.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry, University of Wisconsin─Madison, Madison, Wisconsin 53706, United States.
Herein, we introduce a new platform for alkene carboxy-alkylation. This reaction is designed around CO addition to alkenes followed by radical polar crossover, which enables alkylation through carbanion attack on carbonyl electrophiles. We discovered that CO adds to alkenes faster than it reduces carbonyl electrophiles and that this reactivity can be exploited by accessing CO via hydrogen atom transfer from formate.
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