Diphenyldiazomethane and a labile chlorobenzene complex of [(η-CH)Re(NO)(PPh)] BF react to give the η adduct [(η-CH)Re(NO)(PPh)(NNCPh)] BF (73%). When this is conducted in the presence of copper powder, a 3-phenyl-1-indazole complex derived from carbon-hydrogen bond activation, [(η-CH)Re(NO)(PPh)(NC(Ph)CCHCHCHCHCNH)] BF, is obtained (65%). Subsequent reaction with NaOCH gives indazolyl complex (η-CH)Re(NO)(PPh)(NCCHCHCHCHCC(Ph)N) (85%), derived from NH deprotonation and a 1,2-rhenium shift. Crystal structures of the three new complexes are determined. DFT calculations are used to probe the mechanism of the 1,2-shift and energetics of alternative Re-N rotamers and linkage isomers, and assign bond orders and dominant resonance formulations.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/d2dt00890d | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Novel Catalyst-Free Synthesis of Some 3-Alkylaminoquinoxaline-2(1)-thiones and 3-Alkyloxyquinoxaline-2(1)-thiones in Ethanol.
ACS Omega
January 2025
School of Chemistry, University of Southampton, Southampton SO17 1BJ, United Kingdom.
Seventeen 3-alkylaminoquinoxaline-2(1)-thiones and 3-alkyloxyquinoxaline-2(1)-thiones were prepared by a novel thionation protocol from the readily available quinoxaline-2,3-dione in excellent overall yields. This protocol starts with the chlorination of dione using thionyl chloride to give 2,3-dichloroquinoxaline followed by the reaction with equimolar amounts of -nucleophiles (primary amines and secondary amines) or -nucleophiles (phenols and alcohols) to principally afford 2-alkanamino-3-chloroquinoxalines or 2-alkyloxy-3-chloroquinoxalines, respectively. The chloroquinoxalines reacted with the thionation reagent -cyclohexyl dithiocarbamate cyclohexyl ammonium salt in ethanol under reflux to principally give the corresponding quinoxalin-2-yl cyclohexylcarbamodithioate that finally rearranges to give the corresponding thiones in 76-93% overall yields.
View Article and Find Full Text PDFp97 Inhibitors Possessing Antiviral Activity Against SARS-CoV-2 and Low Cytotoxicity.
Pharmaceuticals (Basel)
January 2025
Center for Drug Design, College of Pharmacy, University of Minnesota, Minneapolis, MN 55455, USA.
p97 (also known as valosin-containing protein, VCP) is a member of the AAA+ ATPase family and is intimately associated with protein quality control and homeostasis regulation. Therefore, pharmaceutical inhibition of p97 has been actively pursued as an anticancer strategy. Recently, p97 has emerged as an important pro-viral host factor and p97 inhibitors are being evaluated as potential antiviral agents.
View Article and Find Full Text PDFCytotoxic Activity of Bisphosphonic Derivatives Obtained by the Michaelis-Arbuzov or the Pudovik Reaction.
Pharmaceuticals (Basel)
January 2025
Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3, 1111 Budapest, Hungary.
Methylenebisphosphonic derivatives including hydroxy-methylenebisphosphonic species may be of potential biological activity, and a part of them is used in the treatment of bone diseases. Methylenebisphosphonates may be obtained by the Michaelis-Arbuzov reaction of suitably α-substituted methylphosphonates and trialkyl phosphites or phosphinous esters, while the hydroxy-methylene variations are prepared by the Pudovik reaction of α-oxophosphonates and different >P(O)H reagents, such as diethyl phosphite and diarylphosphine oxides. After converting α-hydroxy-benzylphosphonates and -phosphine oxides to the α-halogeno- and α-sulfonyloxy derivatives, they were utilized in the Michaelis-Arbuzov reaction with trialkyl phosphites and ethyl diphenylphosphinite to afford the corresponding bisphosphonate, bis(phosphine oxide) and phosphonate-phosphine oxide derivatives.
View Article and Find Full Text PDFAcral Melanoma: A Review of Its Pathogenesis, Progression, and Management.
Biomolecules
January 2025
Department of Dermatology, Wellman Center for Photomedicine, Massachusetts General Hospital, Harvard Medical School, Boston, MA 02114, USA.
Acral melanoma is a distinct subtype of cutaneous malignant melanoma that uniquely occurs on ultraviolet (UV)-shielded, glabrous skin of the palms, soles, and nail beds. While acral melanoma only accounts for 2-3% of all melanomas, it represents the most common subtype among darker-skinned, non-Caucasian individuals. Unlike other cutaneous melanomas, acral melanoma does not arise from UV radiation exposure and is accordingly associated with a relatively low tumor mutational burden.
View Article and Find Full Text PDFDeep Learning-Based Multi-View Projection Synthesis Approach for Improving the Quality of Sparse-View CBCT in Image-Guided Radiotherapy.
J Imaging Inform Med
January 2025
School of Electronic and Information Engineering, Beijing Jiaotong University, Beijing, China.
While radiation hazards induced by cone-beam computed tomography (CBCT) in image-guided radiotherapy (IGRT) can be reduced by sparse-view sampling, the image quality is inevitably degraded. We propose a deep learning-based multi-view projection synthesis (DLMPS) approach to improve the quality of sparse-view low-dose CBCT images. In the proposed DLMPS approach, linear interpolation was first applied to sparse-view projections and the projections were rearranged into sinograms; these sinograms were processed with a sinogram restoration model and then rearranged back into projections.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!