The traditional use of phosphorus compounds is as ligands for transition metals, however herein we synthesize Lewis acidic fluorophosphonium cation appended to a palladium complex and effect CO insertion into a Pd-C bond to obtain an unprecedented metal-benzoyl derived phosphorane.
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http://dx.doi.org/10.1039/c6cc08561j | DOI Listing |
J Org Chem
September 2024
School of Chemistry, University of Glasgow, Joseph Black Building, University Avenue, Glasgow G12 8QQ, U.K.
Conjugate addition of unstabilized Wittig-type phosphonium ylides to 1,1-diacceptor- and 1-acceptor-substituted alkenes is investigated by density functional theory and high-level (DLPNO-CCSD(T)) calculations. The results indicate that the initial conjugate addition step should be facile with barriers predicted to be between 0 and 21 kcal mol. Potential intramolecular follow-up reactions include the formation of acceptor-substituted cyclopropanes as well as the formation of dihydrofuran derivatives via intramolecular S2-type transition state structures.
View Article and Find Full Text PDFOrg Lett
December 2023
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H 4R2, Canada.
We report a versatile method for C2 functionalization of (benz)oxazoles and (benzo)thiazoles employing a -butylimino-tri(pyrrolidino)phosphorane/sodium trifluoroacetate (BTPP/NaTFA) "dual-base" system in combination with an air-stable Ni(II) precatalyst containing either CyPAd-DalPhos or PhPAd-DalPhos. These catalyst systems enable access to a reaction scope that encompasses a range of challenging oxidative addition partners, including (hetero)aryl chlorides as well as pivalates, tosylates, and other related phenol derivatives. The utility of this method is demonstrated through the derivatization of an active pharmaceutical ingredient and 5 mmol synthesis of a thiazole derivative.
View Article and Find Full Text PDFChempluschem
March 2024
Departamento de Química Orgánica, Universidad de Murcia, Campus de Espinardo, 30071, Murcia, Spain.
The deoxygenation of parent and substituted oxiranes by λ σ -phosphorus reagents has been explored in detail, therefore unveiling mechanistic aspects as well as regio- and stereochemical consequences. Attack to a ring C atom is almost always preferred over one-step deoxygenation by direct P-to-O attack. In most cases a carbene transfer occurs as first step, leading to a phosphorane and a carbonyl unit that thereafter react in the usual Wittig fashion via the corresponding λ σ -1,2-oxaphosphetane intermediate.
View Article and Find Full Text PDFDalton Trans
October 2023
Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.
Phospha-Wittig reagents such as phosphanylidene-phosphoranes and their transition metal complexes are of great interest as sources of P building blocks but the access is still limited. Herein, we describe a new access to phosphanylidene-phosphorane complexes starting from the -methylimidazole-to-phosphinidene complex adduct. The complexes were studied electrochemically and theoretically, also with respect to their P NMR data, and the P-P bonds were evaluated by various DFT-derived descriptors.
View Article and Find Full Text PDFInorg Chem
December 2021
Biology Ph.D. Program, The Graduate Center, The City University of New York, New York, New York 10016, United States.
The potential of ruthenium(II) compounds as an alternative to platinum-based clinical anticancer agents has been unveiled after extensive research for over 2 decades. As opposed to cisplatin, ruthenium(II) compounds have distinct mechanisms of action that do not rely solely on interactions with DNA. In a previous report from our group, we described the synthesis, characterization, and biological evaluation of a cationic, water-soluble, organometallic ruthenium(II) iminophosphorane (IM) complex of -cymene, ([(η--cymene)Ru{(PhP═N-CO-2N-CH)-κ-N,O}Cl]Cl ( or Ru-IM), that was found to be highly cytotoxic against a panel of cell lines resistant to cisplatin, including triple-negative breast cancer (TNBC) MDA-MB-231, through canonical or caspase-dependent apoptosis.
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