The ruthenium-catalyzed hydroamidation of terminal alkynes has evolved to become a broadly applicable tool for the synthesis of enamides and enimides. Depending on the catalyst system employed, the reaction leads chemo-, regio-, and stereoselectively to a single diastereoisomer. Herein, we present a comprehensive mechanistic study of the ruthenium-catalyzed hydroamidation of terminal alkynes, which includes deuterium-labeling, in situ IR, in situ NMR, and in situ ESI-MS experiments complemented by computational studies. The results support the involvement of ruthenium-hydride and ruthenium-vinylidene species as the key intermediates. They are best explained by a reaction pathway that consists of an oxidative addition of the amide, followed by insertion of a π-coordinated alkyne into a ruthenium-hydride bond, rearrangement to a vinylidene species, nucleophilic attack of the amide, and finally reductive elimination of the product.
A new series of coumarin and benzofuran derivatives were synthesized as potential non-nucleoside reverse transcriptase inhibitors (NNRTIs) by reacting, separately, 4-bromomethylcoumarins, their sulphonyl chlorides, and ethyl 3-(bromomethyl)-6-methoxy-1-benzofuran-2-carboxylate with different imidazoles and their benzo analogs. The antiviral (HIV-1, HIV-2) properties of the newly synthesized compounds were investigated in vitro and all compounds were found to be inactive, except 10 which showed inhibition of HIV-2 with EC50 > 0.51 μgmL−1. The in vitro cytotoxicity of 17 and 19 was assayed against a panel of tumor cell lines consisting of CD4 human T-cells.
Extremely
small, monodisperse, and spheric maghemite (γ-Fe2O3, 2–3 nm) and manganese (4–7 nm),
cobalt (3–5 nm), and zinc ferrite (5–7 nm) nanocrystals
are directly accessible on a large scale starting from inexpensive
metal powders and octanoic acid by thermolysis in a high-boiling solvent.
Bigger particle size is obtainable by prolonged reaction time according
to the Ostwald ripening principle. The superparamagnetic nanocrystals
and their assembly have been characterized by transmission electron
microscopy, powder X-ray diffraction, Mössbauer spectroscopy,
magnetic measurements, and energy-dispersive X-ray spectroscopy.
A catalyst system generated in situ from bis(2-methallyl)-cycloocta-1,5-diene-ruthenium(II) and a phosphine was found to efficiently catalyze the addition of thioamides to terminal alkynes with exclusive formation of the anti-Markovnikov thioenamide products. The stereoselectivity of the addition is usually high and controlled by the choice of the phosphine ligand, whereas the (E)-isomers are predominantly formed in the presence of tri(n-octyl)phosphine, the use of bis(dicyclohexylphosphino)methane preferentially leads to the formation of the (Z)-configured thioenamides.
Cross-coupling reactions furnishing carbon–carbon (C–C) bond is one of the most challenging tasks in organic syntheses. The early developed reaction protocols by Negishi, Heck, Kumada, Sonogashira, Stille, Suzuki, and Hiyama, utilizing palladium or its salts as catalysis have, for decades, attracted and inspired researchers affiliated with academia and industry. Tremendous efforts have been paid to develop and achieve more sustainable reaction conditions, such as the reduction in energy consumption by applying the microwave irradiation technique. Chemical reactions under controlled microwave conditions dramatically reduce the reaction time and therefore resulting in increase in the yield of the desired product by minimizing the formation of side products. In this review, we mainly focus on the recent advances and applications of palladium catalyzed cross-coupling carbon–carbon bond formation under microwave technology.
A series
of four donor–acceptor conjugated copolymers P1–P4 with linear and branched side chains
based on a ladder-type indacenodithiazole (IDTz) moiety
containing an electron-deficient thiazole unit are copolymerized with
di-2-thienyl-2,1,3-benzothiadiazole (DTBT) and 4,7-di(thien-2-yl)-5,6-difluoro-2,1,3-benzothiadiazole
(DTBTff) as building blocks. Their optical, electrochemical,
and thermal properties and charge transport behavior in organic field-effect
transistors (OFETs) are studied. All copolymers exhibit nearly identical
features in solution with good solubility. In the solid state, P1 does not exhibit a significant shift, while P3 shows a 27 nm red shift, thus illustrating the influence of the
side chain. In the case of copolymers P1 and P2 having linear side chains, there is a clear effect of fluorination
on the film morphology, while it is less pronounced in the case of
polymers P3 and P4 having branched side
chains. All copolymers P1–P4 have
similar highest occupied molecular orbitals regardless of fluorination,
while fluorinated polymers P2 and P4 result
in an increase in the lowest unoccupied molecular orbital. In addition, density functional theory
calculations reveal that the energy levels of IDTz are
down-shifted in comparison to its IDT counterpart containing
an electron-rich thiophene unit. OFETs based on all copolymers exhibit
ambipolar behavior; among the four copolymers, P2 having
a linear dodecyl side chain exhibits remarkable transport properties
with saturated hole mobility as high as 0.87 cm2 V–1 s–1, while P3 exhibits
the highest electron mobility of up to 0.50 cm2 V–1 s–1. Our results set an interesting path to further
utilize the electron-deficient thiazole block in semiconducting materials.
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