A Combined Experimental and Theoretical Study of the Ammonium Bifluoride Catalyzed Regioselective Synthesis of Quinoxalines and Pyrido[2,3-b]pyrazines

International audienceAmmonium bifluoride was efficiently used (at a 0.5 mol % loading) to catalyze the cyclocondensation between 1,2-arylenediamines and 1,2-dicarbonyl compounds at room temperature in methanol-water, affording quinoxalines and pyrido[2,3-b]pyrazines in excellent yields. Importantly, 2,8-disubstituted quinoxalines and 3-substituted pyrido[2,3-b]pyrazines were regioselectively formed by reacting aryl glyoxals with 3-methyl-1,2-phenylenediamine and 2,3-diaminopyridine, respectively. Analysis of the DFT reactivity indices allowed to explain the catalytic role of ammonium bifluoride

Evaluation of Spatial Filtering Algorithms for Visual Interactions in CAVEs

We present an approach to solving the problem of haptic and visual misalignment in CAVEs. The approach moves the collision box for the virtual screen’s buttons to coincide with where the user perceives their virtual location. Different filtering strategies were used.We evaluated the algorithms with simulations and with real subjects

Comparing Tangible and Fully Virtual Haptic Systems for HMI Studies in Simulated Driving Situations

The contribution of tangible and intangible feedback is compared for virtual tactile car Human-Machine Interfaces (HMI) design, to measure their performance both in static conditions and while driving. A subjectively calibrated transparent glass provides tangible passive haptics, and visual cues are used to study sensory substitutionbased intangible interactions. The results show that the performance of the subjects was significantly improved in driving conditions as they interacted faster, more accurately and with a higher satisfaction. In addition, our findings highlight that the contribution of tangible systems is significantly lower in driving conditions, raising new questions about the nature of haptic modalities in the function of the context of use. This study provides additional knowledge about the influence of dynamic environments and external tasks on haptic perception

Comparing Tangible and Fully Virtual Haptic Systems for HMI Studies in Simulated Driving Situations

The contribution of tangible and intangible feedback is compared for virtual tactile car Human-Machine Interfaces (HMI) design, to measure their performance both in static conditions and while driving. A subjectively calibrated transparent glass provides tangible passive haptics, and visual cues are used to study sensory substitution based intangible interactions. The results show that the performance of the subjects was significantly improved in driving conditions as they interacted faster, more accurately and with a higher satisfaction. In addition, our findings highlight that the contribution of tangible systems is significantly lower in driving conditions, raising new questions about the nature of haptic modalities in the function of the context of use. This study provides additional knowledge about the influence of dynamic environments and external tasks on haptic perception

Performance Evaluation of Passive Haptic Feedback for Tactile HMI Design in CAVEs

This article presents a comparison of different haptic systems, which are designed to simulate flat Human Machine Interfaces (HMIs) like touchscreens in virtual environments (VEs) such as CAVEs, and their respective performance. We compare a tangible passive transparent slate to a classic tablet and a sensory substitution system. These systems were tested during a controlled experiment. The performance and impressions from 20 subjects were collected to understand more about the modalities in the given context. The results show that the preferences of the subjects are strongly related to the use-cases and needs. In terms of performance, passive haptics proved to be significantly useful, acting as a space reference and a real-time continuous calibration system, allowing subjects to have lower execution durations and relative errors. Sensory substitution induced perception drifts during the experiment, causing significant performance disparities, demonstrating the low robustness of perception when spatial cues are insufficiently available. Our findings offer a better understanding on the nature of perception drifts and the need of strong multisensory spatial markers for such use-cases in CAVEs. The importance of a relevant haptic modality specifically designed to match a precise use-case is also emphasized

Direct metallation of thienopyrimidines using a mixed lithium-cadmium base and antitumor activity of functionalized derivatives

International audienceA series of thieno[2,3-d]- and thieno[3,2-d]pyrimidines have been easily synthesized using as key step a deproto-cadmiation-trapping sequence. Some of the compounds thus synthesized were screened for anti-cancer (cytotoxic) activities, and (S)-2-(6-iodo-2-phenylthieno[2,3-d]pyrimidin- 4-ylamino)-3-phenylpropanoic acid proved to have a significant activity towards liver, human breast and cervix carcinoma cell lines

Deproto-metallation using mixed lithium-zinc and lithium-copper bases and computed CH acidity of 2-substituted quinolines

International audience2-Substituted quinolines were synthesized, and their deproto-metallation using the bases prepared by mixing LiTMP with either ZnCl2*TMEDA (1/3 equiv) or CuCl (1/2 equiv) was studied. With phenyl and 2-naphthyl substituents, the reaction occurred at the 8 position of the quinoline ring, affording the corresponding iodo derivatives or 2-chlorophenyl ketones using the lithium-zinc or the lithium-copper combination, respectively. With a 4-anisyl substituent, a dideprotonation at the 8 and 3' position was noted using the lithium-zinc base. With 3-pyridyl, 2-furyl and 2-thienyl substituents, the reaction took place on the subtituent, at a position adjacent to its heteroatom. 2-Chlorophenyl 2-phenyl-8-quinolyl ketone could be cyclized under palladium catalysis. The experimental results were analyzed with the help of the CH acidities of the substrates, determined in THF solution using the DFT B3LYP method

Aromatic Iodides: Synthesis and Conversion to Heterocycles

Aromatic heterocycles can be found in many molecules endowed with specific properties, in particular for applications in the fields of medicinal chemistry and materials science. In this group, we notably develop synthetic methodologies to selectively introduce iodine onto aromatic compounds and to use this heavy halogen in order to build heterocycles of interest. While we sometimes employed direct iodinations on electron-enriched aromatic compounds, we mainly optimized deprotometallation–iodolysis sequences to functionalize substrates sensitive to nucleophilic attacks. In particular, hindered lithium amide–metal trap tandems have been designed to overcome the low tolerance of some functional groups (e.g., ketones or sensitive diazines) toward organolithiums. The aromatic iodides generated in these ways have been involved in transition metal–catalyzed cross-couplings to access original scaffolds (oxazoloquinoxalines, pyrazinoisatins, pyrazinocarbazoles, etc.). We specifically developed the use of aromatic iodides in the copper-mediated N-arylation of anilines, e.g., to reach triarylamines. Combined with subsequent cyclizations, these reactions allowed access to numerous heterocyclic compounds (such as acridones, acridines, other aza-aromatic polycycles and helicene-like structures) with potential applications. From some of the scaffolds obtained, biological evaluation in the frame of collaborations allowed properties of interest to be discovered (e.g., specific inhibition of protein kinases GSK-3 or PIM, related to cancer development)

Aromatic Iodides: Synthesis and Conversion to Heterocycles

Proceedings of The 26th International Electronic Conference on Synthetic Organic ChemistryInternational audienceAromatic heterocycles can be found in many molecules endowed with specific properties, in particular for applications in the fields of medicinal chemistry and materials science. In this group, we notably develop synthetic methodologies to selectively introduce iodine onto aromatic compounds and to use this heavy halogen in order to build heterocycles of interest. While we sometimes employed direct iodinations on electron-enriched aromatic compounds, we mainly optimized deprotometallation-iodolysis sequences to functionalize substrates sensitive to nucleophilic attacks. In particular, hindered lithium amide-metal trap tandems have been designed to overcome the low tolerance of some functional groups (e.g., ketones or sensitive diazines) toward organolithiums. The aromatic iodides generated in these ways have been involved in transition metal-catalyzed crosscouplings to access original scaffolds (oxazoloquinoxalines, pyrazinoisatins, pyrazinocarbazoles, etc.). We specifically developed the use of aromatic iodides in the copper-mediated N-arylation of anilines, e.g., to reach triarylamines. Combined with subsequent cyclizations, these reactions allowed access to numerous heterocyclic compounds (such as acridones, acridines, other aza-aromatic polycycles and helicene-like structures) with potential applications. From some of the scaffolds obtained, biological evaluation in the frame of collaborations allowed properties of interest to be discovered (e.g., specific inhibition of protein kinases GSK-3 or PIM, related to cancer development)

A convenient synthesis of 3- and 5-amino-1H-pyrazoles via 3(5)-amino-4-(ethylsulfinyl)-1H-pyrazole desulfinylation

International audienceSyntheses of 5-amino-3-aryl- and 3-amino-5-aryl-1H-pyrazoles from β-bromo-α-(ethylsulfanyl)cinnamonitrile are described. The β-bromo-α-(ethylsulfanyl)cinnamonitriles were oxidized with H2O2 to the corresponding β-bromo-α-(ethylsulfinyl)cinnamonitriles. Subsequent treatment of the resulting sulfoxides with hydrazine hydrate or methylhydrazine followed by hydrochloric acid hydrolysis afforded 5-amino-3-aryl- and 3-amino-5-aryl-1H-pyrazoles, respectively, in good yields