Cationic Rh(III) complex [Cp(PMe(3))Rh(SiPh(3))(CH(2)Cl(2))]BAr(4)' (1) activates the carbon-carbon bond of aryl and alkyl cyanides (R-CN, where R = Ph, (4-(CF(3))C(6)H(4)), (4-(OMe)C(6)H(4)), Me, (i)Pr, (t)Bu) to produce complexes of the general formula [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. With the exception of the (t)BuCN case, every reaction proceeds at room temperature (t(1/2) < 1 h for aryl cyanides, t(1/2) < 14 h for alkyl cyanides). A general mechanism is presented on the basis of (1) an X-ray crystal structure determination of an intermediate isolated from the reaction involving 4-methoxybenzonitrile and (2) kinetic studies performed on the C-C bond cleavage of para-substituted aryl cyanides. Initial formation of an eta(1)-nitrile species is observed, followed by conversion to an eta(2)-iminoacyl intermediate, which was observed to undergo migration of R (aryl or alkyl) to rhodium to form the product [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ja034468o | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Diverse Annulations of Alkyl(phenyl)phosphinic Chlorides and Imines.
Org Lett
January 2025
State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China.
The reactivity of alkyl(aryl)phosphinic chlorides and imines was investigated in the presence of a base. The results indicated that allyl/benzyl(aryl)phosphinic chlorides gave rise to 1,2-azaphosphines (δ-phostims), while nonbenzylic alkyl(aryl)phosphinic chlorides produced the corresponding β-phosphinolactams (β-phostims) in their reaction with cyclic dibenzo[,][1,4]oxazepines, whereas steric electron-rich arylmethyl(aryl)phosphinic chlorides generated [2 + 2 + 2] annuloadducts in some cases. The current investigation provides useful insight into the reactivity of phosphinic chlorides and imines.
View Article and Find Full Text PDFHigh-Throughput Zebrafish Screening Reveals Cardiotoxic Effects of Organophosphate Flame Retardants.
Environ Res
January 2025
International Research Center for Marine Biosciences, Shanghai Ocean University, Ministry of Science and Technology, Shanghai 201306, P.R. China; Key Laboratory of Exploration and Utilization of Aquatic Genetic Resources, Ministry of Science and Technology, Shanghai Ocean University, Shanghai 201306, P.R. China; Marine Biomedical Science and Technology Innovation Platform of Lin-gang Special Area, Shanghai 201306, P.R. China. Electronic address:
The toxicity of organophosphorus flame retardants (OPFRs) remains poorly understood, despite their widespread environmental presence and potential risks to human and ecological health. This study aimed to characterize the cardiovascular developmental toxicity of OPFRs using a high-throughput zebrafish screening model. Over thirty representative OPFRs, classified into three major groups-alkyl, aryl, and halogenated-were evaluated.
View Article and Find Full Text PDFModular Access to Chiral Benzylamines via Ni/Photoredox-Catalyzed Multicomponent Cross-Electrophile Coupling.
Org Lett
January 2025
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, Jiangxi 330031, P. R. China.
A Ni/photoredox dual-catalyzed multicomponent cross-electrophile coupling of N-vinyl amides with (hetero)aryl halides and (2°, 3°)-alkyl redox-active esters in the presence of cheap reductant Hantzsch ester is reported here. This reductive protocol provides direct access to various synthetically challenging chiral α-arylamides in good yields and excellent enantioselectivities (up to 99% ee, with the majority exceeding 97% ee), which can be further derived into chiral primary and secondary amines. Preliminary experimental studies shed light on the potential catalytic pathways.
View Article and Find Full Text PDFNew N-Alkylketonetetrahydroisoquinoline derivatives exhibits antitumor effect by HA-CD44 interaction inhibition in MDA-MB-231 breast cancer.
Bioorg Chem
January 2025
Department of Medicinal and Organic Chemistry and Excellence Research Unit of Chemistry Applied to Biomedicine and the Environment, Faculty of Pharmacy, University of Granada, Campus Cartuja s/n 18071 Granada, Spain; Biosanitary Institute of Granada (ibs.GRANADA), SAS-University of Granada, Avenida de Madrid, 15 18012 Granada, Spain. Electronic address:
Molecular interactions at the cell surface, in particular between hyaluronic acid (HA) and the cluster of differentiation 44 (CD44) receptor, are crucial in several biological processes and diseases such as cancer. Thus, inhibition of the HA-CD44 interaction has become a promising therapeutic strategy. Etoposide was the only antitumor compound known to inhibit the binding of CD44 to HA, thereby disrupting key functions that drive malignancy.
View Article and Find Full Text PDFCloning and functional characterization of sesquiterpene synthase genes from Inonotus obliquus using a Saccharomyces cerevisiae expression system.
World J Microbiol Biotechnol
January 2025
Key Laboratory of Biotechnology for Medicinal Plants of Jiangsu Province, School of Life Sciences, Jiangsu Normal University, Xuzhou, 221116, China.
Inonotus obliquus (Chaga mushroom) is a large medicinal and edible fungus that contains a wealth of bioactive terpenoids. However, the detection of certain low-abundance sesquiterpenoids remains a challenge due to limitations in extraction and analytical techniques. Furthermore, the synthase genes responsible for the biosynthesis of the identified terpenoids have not yet been clearly elucidated.
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!