487-19-4Relevant academic research and scientific papers
An improved synthesis of β-Nicotyrine from the dehydrogenation of nicotine: Comparison of conventional and microwave-assisted reactions
Wei, Xiaochen,Crooks, Peter A.
, p. 3305 - 3315 (2003)
β-Nicotyrine, a minor tobacco alkaloid, can be rapidly prepared in good yield from the dehydrogenation of S-(-)-nicotine over MnO2 with microwave irradiation. This method is superior to dehydrogenation reactions that utilize S-(-)-nicotine and MnO2 in a variety of solvents under reflux.
Interconversion of nicotine enantiomers during heating and implications for smoke from combustible cigarettes, heated tobacco products, and electronic cigarettes
Moldoveanu, Serban C.
, p. 667 - 677 (2022/02/02)
Physiological properties of (R)-nicotine have differences compared with (S)-nicotine, and the subject of (S)- and (R)-nicotine ratio in smoking or vaping related items is of considerable interest. A Liquid Chromatography-Mass Spectrometry/Mass Spectrometry (LC-MS/MS) method for the analysis of (S)- and (R)-nicotine has been developed and applied to samples of nicotine from different sources, nicotine pyrolyzates, several types of tobacco, smoke from combustible cigarettes, smoke from heated tobacco products, e-liquids, and particulate matter obtained from e-cigarettes aerosol. The separation was achieved on a Chiracel OJ-3 column, 250 × 4.6 mm with 3-μm particles using a nonaqueous mobile phase. The detection was performed using atmospheric pressure chemical ionization (APCI) in positive mode. The only transition measured for the analysis of nicotine was 163.1 → 84.0. The method has been summarily validated. For the analysis, the samples of tobacco and smoke from combustible cigarettes were subject to a cleanup procedure using solid phase extraction (SPE). It was demonstrated that nicotine upon heating above 450°C for several minutes starts decomposing, and some formation of (R)-enantiomer from a sample of 99% (S)-nicotine is observed. An analogous process takes place when a 99% (R)-nicotine is heated and forms low levels of (S)-nicotine. This interconversion has the effect of slightly increasing the content of (R)-nicotine in smoke compared with the level in tobacco for combustible cigarettes and for heated tobacco products. The (S)/(R) ratio of nicotine enantiomers in e-liquids was identical with the ratio for the particulate phase of aerosols generated by e-cigarette vaping.
C2-Selective silylation of pyridines by a rhodium-aluminum complex
Hara, Naofumi,Uemura, Nao,Nakao, Yoshiaki
supporting information, p. 5957 - 5960 (2021/06/18)
We have developed a C2-selective mono-silylation of a variety of pyridines using a Rh-Al complex. Both the site- and mono-selectivity are controlledviathe pyridine coordination to the Lewis-acidic Al center prior to the activation of the pyridine C(2)-H bond at the proximal Rh center. A reaction mechanism is proposed based on several mechanistic studies, including the isolation of a (2-pyridyl)silylrhodium intermediate.
Copper catalysed Gomberg-Bachmann-Hey reactions of arenediazonium tetrafluoroborates and heteroarenediazonium o-benzenedisulfonimides. Synthetic and mechanistic aspects
Antenucci, Achille,Barbero, Margherita,Dughera, Stefano,Ghigo, Giovanni
, (2020/10/20)
Gomberg-Bachmann-Hey reactions were carried out in the presence of copper as a catalyst and gave rise to biaryls or heterobiaryls in good yields and in mild reaction conditions. A computational study of some key points of the reaction was performed. The results are coherent with the experimental data and confirm some aspects of the mechanism. The reaction free energies for the reduction in benzene by CuI of a set of 40 (hetero)arenediazonium tetrafluoroborates were calculated. Both the experiments and the calculations showed that in the coupling with substituted solvents (toluene, bromobenzene, nitrobenzene and anisole) the binding to the ortho position was always favoured.
A case of chain propagation: α-aminoalkyl radicals as initiators for aryl radical chemistry
Constantin, Timothée,Juliá, Fabio,Leonori, Daniele,Sheikh, Nadeem S.
, p. 12822 - 12828 (2020/12/29)
The generation of aryl radicals from the corresponding halides by redox chemistry is generally considered a difficult task due to their highly negative reduction potentials. Here we demonstrate that α-aminoalkyl radicals can be used as both initiators and chain-carriers for the radical coupling of aryl halides with pyrrole derivatives, a transformation often employed to evaluate new highly reducing photocatalysts. This mode of reactivity obviates for the use of strong reducing species and was also competent in the formation of sp2 C-P bonds. Mechanistic studies have delineated some of the key features operating that trigger aryl radical generation and also propagate the chain process.
UVA- and Visible-Light-Mediated Generation of Carbon Radicals from Organochlorides Using Nonmetal Photocatalyst
Matsubara, Ryosuke,Yabuta, Tatsushi,Md Idros, Ubaidah,Hayashi, Masahiko,Ema, Fumitoshi,Kobori, Yasuhiro,Sakata, Ken
, p. 9381 - 9390 (2018/07/25)
Carbon radicals are reactive species useful in various organic transformations. The C-X bond cleavage of organohalides by photoirradiation is a common method to generate carbon radicals in a controlled fashion. The use of organochloride substrates is still a formidable challenge due to the low reduction potential and the high dissociation energy of the C-Cl bond. In this report, we address these issues by using a nonmetal organic molecule with a relatively simple structure as a photocatalyst. In this catalyst (bis(dimethylamino)carbazole), the amino groups increase both the HOMO and LUMO energy levels, especially in the former. As a result, compared to the parent molecule, the new catalyst shows experimentally red-shifted absorption in the visible region and forms an excited state with better reducing capability. This photocatalyst was used in the reduction of unactivated aryl chlorides and alkyl chlorides in the presence of hydrogen atom donor at room temperature. The catalytic system can also be applied to the coupling of aryl chlorides with electron-rich arene and heteroarenes to affect the C-C bond-forming reactions. Our mechanistic study results support the assumption that carbon radicals are formed from the organochlorides via a single-electron-transfer step.
A general copper-based photoredox catalyst for organic synthesis: Scope, application in natural product synthesis and mechanistic insights
Deldaele, Christopher,Michelet, Bastien,Baguia, Hajar,Kajouj, Sofia,Romero, Eugenie,Moucheron, Cecile,Evano, Gwilherm
, p. 621 - 629 (2018/10/04)
Organic transformations can broadly be classified into four categories including cationic, anionic, pericyclic and radical reactions. While the last category has been known for decades to provide remarkably efficient synthetic pathways, it has long been hampered by the need for toxic reagents, which considerably limited its impact on chemical synthesis. This situation has come to an end with the introduction of new concepts for the generation of radical species, photoredox catalysis – which simply relies on the use of a catalyst that can be activated upon visible light irradiation – certainly being the most efficient one. The state-of-the-art catalysts mostly rely on the use of ruthenium and iridium complexes and organic dyes, which still considerably limits their broad implementation in chemical processes: alternative readily available catalysts based on inexpensive, environmentally benign base metals are therefore strongly needed. Furthermore, expanding the toolbox of methods based on photoredox catalysis will facilitate the discovery of new light-mediated transformations. This article details the use of a simple copper complex which, upon activation with blue light, can initiate a broad range of radical reactions.
Dichromatic Photocatalytic Substitutions of Aryl Halides with a Small Organic Dye
Neumeier, Michael,Sampedro, Diego,Májek, Michal,de la Pe?a O'Shea, Víctor A.,Jacobi von Wangelin, Axel,Pérez-Ruiz, Raúl
supporting information, p. 105 - 108 (2017/12/04)
Photocatalytic bond activations are generally limited by the photon energy and the efficiency of energy and electron transfer processes. Direct two-photon processes provide sufficient energy but the ultra-short lifetimes of the excited states prohibit chemical reactions. The commercial dye 9,10-dicyanoanthracene enabled photocatalytic aromatic substitutions of non-activated aryl halides. This reaction operates under VIS-irradiation via sequential photonic, electronic, and photonic activation of the simple organic dye. The resultant highly reducing excited photocatalyst anion readily effected C?H, C?C, C?P, C?S, and C?B bond formations. Detailed synthetic, spectroscopic, and theoretical studies support a biphotonic catalytic mechanism.
A General Copper Catalyst for Photoredox Transformations of Organic Halides
Michelet, Bastien,Deldaele, Christopher,Kajouj, Sofia,Moucheron, Cécile,Evano, Gwilherm
supporting information, p. 3576 - 3579 (2017/07/17)
A broadly applicable copper catalyst for photoredox transformations of organic halides is reported. Upon visible light irradiation in the presence of catalytic amounts of [(DPEphos)(bcp)Cu]PF6 and an amine, a range of unactivated aryl and alkyl halides were shown to be smoothly activated through a rare Cu(I)/Cu(I)?/Cu(0) catalytic cycle. This complex efficiently catalyzes a series of radical processes, including reductions, cyclizations, and direct arylation of arenes.
Quantum Dots in Visible-Light Photoredox Catalysis: Reductive Dehalogenations and C-H Arylation Reactions Using Aryl Bromides
Pal, Anuushka,Ghosh, Indrajit,Sapra, Sameer,K?nig, Burkhard
, p. 5225 - 5231 (2017/07/04)
In the recent past, visible-light-mediated photoredox catalysis has made a huge impact on the development of new synthetic methods under very mild and ecologically benign conditions. Although semiconductor nanocrystals or quantum dots (QDs) possess suitable optoelectronic and redox properties for photoredox catalytic applications, surprisingly, their use for the activation of challenging chemical bonds in the synthesis of organic molecules is little explored. We report here the application of ZnSe/CdS core/shell QDs for the synthetically important photoredox catalytic activation of carbon-halogen bonds in dehalogenation and C-H arylation reactions using (hetero)aryl halides as bench-stable inexpensive bulk starting materials, under very mild reaction conditions. The outstanding catalytic activity of ZnSe/CdS core/shell QDs is a direct consequence of the high specific surface area and homogeneity of QDs in solution and their high photostability toward oxidation.
