Synthesis of Bifunctional Amine-Squaramide Organocatalysts Derived from 3-((Dimethylamino)methylene)camphor.

Four bifunctional, noncovalent amine-squaramide organocatalysts were prepared from camphor in five steps. The stereochemistry of the prepared catalysts was thoroughly analyzed using various spectroscopic techniques. Their organocatalytic activity was investigated in the Michael addition of acetylacetone to trans-ß-nitrostyrene. The addition product was formed in complete conversion and with an enantioselectivity of up to 77% ee. In the reactions catalyzed by the 2-exo-3-endo catalysts, the major (S)-enantiomer was formed, whereas in the presence of 2-endo-3-endo catalysts, the (R)-enantiomer was formed as the major product.

Synthesis of Six-Membered N-Heterocyclic Carbene Precursors Based on Camphor.

The endo- and exo-N-heterocyclic carbene precursors based on camphor were prepared diastereoselectively in five synthetic steps starting from (1S)-(+)-ketopinic acid. The obtained N-heterocyclic carbene precursors were investigated in an asymmetric benzoin reaction. All new compounds were fully characterized, and the absolute configurations were determined via X-ray diffraction and NOESY measurements.

Catalytic Photoredox C-H Arylation of 4-Oxo-4H-pyrido[1,2-a]pyrimidine-3-diazonium Tetrafluoroborates and Related Heteroaryl Diazonium Salts.

Irradiation of mixtures of title diazonium salts and heteroarenes with green light (510 nm) in the presence of eosin Y disodium salt (EY-Na2) as a photocatalyst furnished the corresponding arylation products in 8-63% yields. The proposed photocatalytic cycle is analogous to that proposed previously for closely related photoredox C-H arylations with aryl diazonium salts as aryl radical sources. This method has a broad substrate scope and represents a metal-free alternative for the synthesis of 3-heteroaryl-substituted 4H-quinolizin-4-ones and azino- and azolo-fused pyrimidones with a bridgehead nitrogen atom.

Synthesis and Catalytic Activity of Bifunctional Phase-Transfer Organocatalysts Based on Camphor.

Ten novel bifunctional quaternary ammonium salt phase-transfer organocatalysts were synthesized in four steps from (+)-camphor-derived 1,3-diamines. These quaternary ammonium salts contained either (thio)urea or squaramide hydrogen bond donor groups in combination with either trifluoroacetate or iodide as the counteranion. Their organocatalytic activity was evaluated in electrophilic heterofunctionalizations of ß-keto esters and in the Michael addition of a glycine Schiff base with methyl acrylate. α-Fluorination and chlorination of ß-keto esters proceeded with full conversion and low enantioselectivities (up to 29% ee). Similarly, the Michael addition of a glycine Schiff base with methyl acrylate proceeded with full conversion and up to 11% ee. The new catalysts have been fully characterized; the stereochemistry at the C-2 chiral center was unambiguously determined.

Copper- and Photoredox-Catalyzed Cascade to Trifluoromethylated Divinyl Sulfones.

A Cu(I)-photoredox-catalyzed trifluoromethylchlorosulfonylation reaction of terminal alkynes under visible light conditions was developed, giving rise to trifluoromethyl-substituted vinylsulfonyl chlorides, which can subsequently be coupled to a second alkyne under photocatalytic conditions. The transformation proceeds with high regio- and stereoselectivity and can be applied to aliphatic and aromatic alkynes with various functional groups. Trifluoromethyl-substituted divinyl sulfones prepared by this protocol can be readily used as synthetically valuable intermediates as demonstrated with various postmodification examples.

Seasonal variability of nitroaromatic compounds in ambient aerosols: Mass size distribution, possible sources and contribution to water-soluble brown carbon light absorption.

Nitroaromatic compounds (NACs) as important constituents of atmospheric humic-like substances (HULIS) and brown carbon (BrC) affect the Earth's climate and pose a serious environmental hazard. We investigated seasonal size-segregated NACs in aerosol samples from the urban background environment in Ljubljana, Slovenia. Total concentrations of twenty NACs in PM15.6 were on average from 0.51 ng m-3 (summer) to 109 ng m-3 (winter), and contributed the most to submicron aerosols (more than 74%). Besides 4-nitrocatechol (4NC) as the prevailing species, methylnitrocatechols (MNCs) and nitrophenols (NPs), we reported on some very rarely mentioned, but also on five novel NACs (i.e., 3H4NBA: 3-hydroxy-4-nitrobenzoic acid, 3MeO4NP: 3-methoxy-4-nitrophenol, 4Et5NC: 4-ethyl-5-nitrocatechol, 3Et5NC: 3-ethyl-5-nitrocatechol and 3MeO5NC: 3-methoxy-5-nitrocatechol). Concentrations of 3MeO5NC, 4Et5NC and 3Et5NC were enhanced during cold seasons, contributing up to 11% to total NAC in winter. In cold season, NAC size distributions were characterized with the peaks in the broader size range of 0.305-1.01 µm (accumulation mode), with 4NC and alkyl-nitrocatechols (∑(M/Et)NC) as the most abundant, followed by 4-nitrosyringol, nitrophenols and nitroguaiacols. In spring, a pronounced peak of ∑(M/Et)NC was observed in the accumulation mode (0.305-0.56 µm) as well as in the coarse one. A strong correlation of all NACs with ∑(M/Et)NC and levoglucosan indicates that primary emissions of wood burning were the most important source of NACs, but their secondary formation (e.g., aqueous-phase at higher ambient RH) in cold season could also be a significant one. In warmer season, NACs may be mostly derived from traffic-related aromatic VOCs. The contribution of NACs to the light absorption of the aqueous extracts was up to 10-times higher (contribution to Abs365 up to 31%) than their mass contributions to WSOC (up to 3%) of corresponding size-segregated aerosols, confirming that most of the identified NACs are strong BrC chromophores.

Visible-Light Driven Selective C-N Bond Scission in anti-Bimane-Like Derivatives.

In the present study, we report the photochemical transformation of pyrazolo[1,2-a]pyrazolone substrates that reach an excited state upon irradiation with visible light to initiate the homolytic C-N bond cleavage process that yields the corresponding N1-substituted pyrazoles. Moreover, chemoselective heterolytic C-N bond cleavage is possible in the pyrazolo[1,2-a]pyrazole core in the presence of bromomalonate.

Regioselective Ru(II)/Pd(0) Dual Catalysis: One-Pot C-H Diarylation of Five-Membered Heterocyclic Derivatives.

Herein, we report a one-pot site-selective dual metal catalyzed C-H diarylation reaction for the synthesis of multiarylated thiophene and furan derivatives in yields up to 92%. The regioselectivity of the developed methodology was achieved with the sequential use of two metal catalysts within a single vessel, starting with a Ru(II)-catalyzed C3 arylation assisted by an azine directing group, followed by a Pd(0)-catalyzed C-H functionalization on the C5-position of the five-membered heterocycle. Furthermore, the kinetic studies support that the position of the nitrogen atom within the azine moiety exhibits an evident effect on the efficiency of the ruthenium-catalyzed arylation step.

Improving the Chemical Selectivity of an Electronic Nose to TNT, DNT and RDX Using Machine Learning.

We used a 16-channel e-nose demonstrator based on micro-capacitive sensors with functionalized surfaces to measure the response of 30 different sensors to the vapours from 11 different substances, including the explosives 1,3,5-trinitro-1,3,5-triazinane (RDX), 1-methyl-2,4-dinitrobenzene (DNT) and 2-methyl-1,3,5-trinitrobenzene (TNT). A classification model was developed using the Random Forest machine-learning algorithm and trained the models on a set of signals, where the concentration and flow of a selected single vapour were varied independently. It is demonstrated that our classification models are successful in recognizing the signal pattern of different sets of substances. An excellent accuracy of 96% was achieved for identifying the explosives from among the other substances. These experiments clearly demonstrate that the silane monolayers used in our sensors as receptor layers are particularly well suited to selecting and recognizing TNT and similar types of explosives from among other substances.

Synthesis of 8-heteroaryl nitroxoline analogues via one-pot sequential Pd-catalyzed coupling reactions.

A series of 8-heteroaryl substituted quinolines were prepared, either by direct C-H arylation of five-membered heteroarenes, or Pd-catalyzed coupling of organoboron reagents with bromoquinolines. The use of (benzo)thiophenyl or (benzo)furanyl boron coupling partners allowed further C-H functionalization on the five-membered heteroaryl ring with aryl bromides in one flask to access a variety of polyconjugated molecular architectures. The developed methodology represents a simple approach towards 8-arylated analogues of the biologically interesting nitroxoline core.