A synthesis of highly functionalized nitroalkenes is reported that utilizes a cross metathesis (CM) reaction between simple aliphatic nitro compounds and a range of substituted alkenes. This chemistry offers a simple and attractive route to nitroalkenes that would otherwise be difficult to prepare, and that have a very useful application as precursors to a variety of heterocyclic entities.
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http://dx.doi.org/10.1021/ol070557k | DOI Listing |
ACS Omega
December 2024
Division of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
A Hoveyda-Grubbs (HG)-type olefin metathesis complex with a selenoether moiety at the terminus of phenoxy moiety was synthesized. The complex showed direct selenium-atom coordination to the ruthenium center, resulting in higher thermodynamic stability compared with the parent HG catalyst. The selenium atom binding enhanced the tolerance to protic solvent molecules in ring-closing metathesis of -tosyldiallylamide and diethyl diallylmalonate, and also in the cross metathesis between 3-butenylbenzoate and methyl acrylate.
View Article and Find Full Text PDFLangmuir
December 2024
Department of Chemistry, Carnegie Mellon University, 4400 Avenue, Pittsburgh, Pennsylvania 15213, United States.
Structurally tailored and engineered macromolecular (STEM) networks are attractive materials for soft robotics, stretchable electronics, tissue engineering, and 3D printing due to their tunable properties. To date, STEM networks have been synthesized by atom transfer radical polymerization (ATRP) or the combination of reversible addition-fragmentation chain-transfer (RAFT) polymerization and ATRP. RAFT polymerization could have limited selectivity with ATRP inimer sites that can participate in radical-transfer processes.
View Article and Find Full Text PDFPhys Chem Chem Phys
December 2024
Department of Chemistry, CMS College Kottayam (Autonomous) Mahatma Gandhi University, Kottayam, Kerala, 686001, India.
A detailed theoretical study delving into the molecular mechanisms of the Ullmann-type -arylation reactions catalyzed by manganese and zinc metal ions has been investigated with the aid of the density functional theory (DFT) method. In contrast to the redox-active mechanisms proposed for classical Ullmann-type condensation reaction, a redox-neutral mechanism involving σ-bond metathesis emerged as the most appealing pathway for the investigated high-valent Mn(II) and Zn(II)-catalyzed -arylation reactions. The mechanism remains invariant with respect to the nature of the central metal, ligand, base, This unusuality in the mechanism has been dissected by considering three cases: ligand-free and ligand-assisted Mn(II)-catalyzed -arylation reaction and ligand-assisted Zn(II)-catalyzed -arylation reactions.
View Article and Find Full Text PDFJ Nat Prod
December 2024
Department of Chemistry, University of Kalyani, Kalyani 741235 West Bengal, India.
A concise synthetic route to an epimer of the recently isolated biologically active cyclic tetrapeptide koshidacin B has been developed, which featured a late-stage functionalization of a macrocyclic scaffold through a cross metathesis reaction. The synthetic 9--koshidacin B showed marginal differences in spectroscopic behavior with that of the natural product but exhibited conformational preferences similar to those reported for analogous substrate chlamydocin. Moreover, it exhibited a useful level of selective inhibition of biologically relevant enzyme histone deacetylase 1 with an IC value of 0.
View Article and Find Full Text PDFJ Org Chem
December 2024
College of Pharmacy & Graduate School of Pharmaceutical Sciences, Ewha Womans University, 52 Ewhayeodae-gil, Seodaemun-Gu, Seoul 03760, Republic of Korea.
The concise and efficient total synthesis of (±)-tetraponerine-2 () and (±)-tetraponerine-4 () was achieved in 9% and 14% overall yield, respectively. The key step included the diastereoselective gold(I)-catalyzed intramolecular dehydrative amination of an allylic alcohol-tethered sulfamide to produce the 1,3-diamine moiety. The resulting olefinic side chain was then elaborated by cross-metathesis and cyclized to a five-membered pyrrolidine or a six-membered piperidine ring by intramolecular Mitsunobu -alkylation.
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