AI Article Synopsis
Article Abstract
The first N-tritylpyrrolidino derivatives of D(3h) (78:5) Sc(3)N@C(78) were successfully synthesized and isolated. The addition sites for the two nearly equivalent kinetic monoadducts 1a and 1b are across two different 6,6 junction sites on the Sc(3)N@C(78) cage that are offset from the horizontal plane defined by the Sc(3)N cluster. The adducts were characterized by NMR experiments, DFT calculations and X-ray crystallographic analysis of Sc(3)N@C(78) derivative 1a. A unique finding of this study is the regiocontrol of adduct docking by the internal Sc(3)N cluster.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ja072345o | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
The Origin of Catalysis and Regioselectivity of Lewis Acid-Catalyzed Diels-Alder Reactions with Tropone.
Chemistry
July 2023
Department of Chemistry and Pharmaceutical Sciences, AIMMS, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam (The, Netherlands.
We have studied the uncatalyzed and Lewis acid (LA)-catalyzed cycloaddition reaction between tropone and 1,1-dimethoxyethene using dispersion-corrected relativistic density functional theory (DFT). The LA catalysts BF , B(C H ) , and B(C F ) efficiently accelerate both the competing [4+2] and [8+2] cycloaddition reactions by lowering the activation barrier up to 12 kcal mol compared to the uncatalyzed reaction. Our study reveals that the LA catalyst promotes both cycloaddition reaction pathways by LUMO-lowering catalysis and demonstrates that Pauli-lowering catalysis is not always the operative catalytic mechanism in cycloaddition reactions.
View Article and Find Full Text PDFOxidative two-way regiocontrolled coupling of 3-methoxycarbonylcatechol and indoles to arylindoles.
Chem Commun (Camb)
November 2022
A Laboratory of Organic Chemistry, Gifu Pharmaceutical University, 1-25-4-Daigaku-nishi, Gifu 501-1196, Japan.
3-Methoxycarbonylcatechol effectively underwent two-way regiocontrolled coupling with indoles an -benzoquinone intermediate, resulting from phenyliodine(III) diacetate oxidation, to generate 4-adducts or 5-adducts with or without BF·EtO in a one-pot manner. DFT calculations confirmed the obtained regioselectivities.
View Article and Find Full Text PDFTuning the Regioselectivity of Topochemical Polymerization through Cocrystallization of the Monomer with an Inert Isostere.
Angew Chem Int Ed Engl
October 2022
School of Chemistry, IISER Thiruvananthapuram, Kerala, 695551, India.
Regiochemistry of topochemical reactions depends on the crystal packing and biasing the regiochemistry necessitates precise crystal engineering. The pristine crystals of monomer 1 upon topochemical azide-alkyne cycloaddition (TAAC) reaction give a 1 : 1 blend of 1,4- and 1,5-triazole-linked polymers due to the presence of two self-sorted reactive conformers in the crystal. We designed a binary isomorphous cocrystal of monomer 1 and a structurally similar dummy molecule 2 to limit the number of reactive conformers of 1 to one and thus to get one type of polymer.
View Article and Find Full Text PDFAccess to a pair of ambiphilic phosphine-borane regioisomers by rhodium-catalyzed hydroboration.
Dalton Trans
June 2018
C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, West Virginia 26505, USA.
Lewis basic substrates, such as vinylphosphines and enamines, can be problematic for transition-metal catalysed hydrofunctionalization reactions due to their propensity to ligate and deactivate transition-metal catalysts as well as form direct Lewis adducts with reaction partners. While exploring rhodium-catalyzed hydroboration of diphenylvinylphosphine with pinacolborane, we found that a high degree of regiocontrol could be achieved without the need to diminish the Lewis basicity of the phosphine by oxidation or prior-protection. At slightly elevated temperature, a high yield of the previously unreported branched regioisomer, 1-pinacolatoborono-1-diphenylphosphinoethane, was achieved with regioselectivity greater than 10 : 1 using [Rh(COD)Cl]2 as the catalyst and AgOTf as a catalytic additive.
View Article and Find Full Text PDFPalladacycle promoted base controlled regio- and enantioselective hydrophosphination of 2-pyridylacrylate/amide and the cytotoxicity of their gold complexes.
Dalton Trans
October 2015
Division of Chemistry & Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637616.
The regioselective asymmetric hydrophosphination of pyridine-functionalized alkenes can be achieved in the presence of stoichiometric amounts of the chiral palladium complex (R)-1. The presence or absence of base affords the respective β- and α-adducts with excellent regiocontrol. Chiral gold-phosphine complexes incorporating the adducts exhibited good in vitro anticancer activity against the breast cancer cell line MDA-MB-231.
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!