4831-01-0Relevant articles and documents
N-Atom Deletion in Nitrogen Heterocycles
Cai, Wangshui,Guo, Ting,Li, Guigen,Lu, Hongjian,Qin, Haitao,Wang, Shuang
, p. 20678 - 20683 (2021/08/25)
Excising the nitrogen in secondary amines, and coupling the two residual fragments is a skeletal editing strategy that can be used to construct molecules with new skeletons, but which has been largely unexplored. Here we report a versatile method of N-atom excision from N-heterocycles. The process uses readily available N-heterocycles as substrates, and proceeds by N-sulfonylazidonation followed by the rearrangement of sulfamoyl azide intermediates, providing various cyclic products. Examples are provided of deletion of nitrogen from natural products, synthesis of chiral O-heterocycles from commercially available chiral β-amino alcohols, formal inert C?H functionalization through a sequence of N-directed C?H functionalization and N-atom deletion reactions in which the N-atom can serve as a traceless directing group.
Iron-Catalyzed Remote Arylation of Aliphatic C-H Bond via 1,5-Hydrogen Shift
Zhou, Bingwei,Sato, Hiroki,Ilies, Laurean,Nakamura, Eiichi
, p. 8 - 11 (2018/01/17)
Catalytic amounts of an iron(III) salt and a N-heterocyclic carbene ligand catalyze the arylation of 2-iodoalkylarenes with diphenylzinc selectively at the C-H bond of the alkyl side chain. Several lines of evidence suggest that the iron catalyst reacts with the aryl iodide moiety of the substrate to generate an aryliron intermediate that behaves in a radical manner and cleaves the aliphatic C-H bond through 1,5-hydrogen transfer; the resulting alkyliron intermediate undergoes reductive elimination to give the arylated product.
Catalytic Use of Low-Valent Cationic Gallium(I) Complexes as π-Acids
Li, Zhilong,Thiery, Guillaume,Lichtenthaler, Martin R.,Guillot, Régis,Krossing, Ingo,Gandon, Vincent,Bour, Christophe
supporting information, p. 544 - 549 (2017/11/27)
Transformations of alkene and alkyne substrates relevant to π-Lewis acid catalysis have been performed using low-valent Ga(I) species for the first time. [Ga(I)(PhF)2]+[Al(ORF)4]? and gallium dichloride (i. e. [Ga(I)]+[GaCl4]?) proved to be efficient catalysts for cycloisomerizations, Friedel-Crafts reactions, transfer hydrogenations, and reductive hydroarylations. Their activity is compared to more common Ga(III) complexes. This study shows that even the readily available and yet overlooked gallium dichloride salt can be a more active π-Lewis acid catalyst than gallium trichloride or other Ga(III) species. (Figure presented.).
Gallium-assisted transfer hydrogenation of alkenes
Michelet, Bastien,Bour, Christophe,Gandon, Vincent
, p. 14488 - 14492 (2015/04/16)
We report a rare case of alkene transfer hydrogenation using a main-group compound instead of a transition-metal complex as catalyst. We disclosed that 1, 4-cyclo-hexadiene can be used as H2 surrogate towards olefin reduction in the presence of [IPrGaCl2][SbF6]. Hydrogenative cycli-zations have also been carried out because this cationic gallium complex is also a potent hydroarylation catalyst.
Structural effects in radical clocks and mechanisms of grignard reagent formation: Special effect of a phenyl substituent in a radical clock when the crossroads of selectivity is at a metal/solution interface
Hazimeh, Hassan,Mattalia, Jean-Marc,Marchi-Delapierre, Caroline,Kanoufi, Frederic,Combellas, Catherine,Chanon, Michel
experimental part, p. 2775 - 2787 (2009/08/16)
A large class of radical clocks is based on the intramolecular trapping of a reactive radical by a suitably located, unsaturated system. Depending on the substituents present on this unsaturated system, the rate of cyclisation may vary drastically. This property has been repeatedly used, to diagnose the participation of very short-lived radicals in the mechanisms of a wide variety of reactions. For reactions occurring in homogeneous solution, a phenyl substituent capable of stabilizing the radical formed during the act of trapping has been one of the most widely used tools of this type. During study of the mechanisms of formation of Grignard reagents - reactions that occur at the interface of the metal and the solution - the phenyl substituent displayed a specific new behaviour pattern. Besides its stabilizing role, it was also able to play the role of mediator in redox catalysis of electron transfer. In this case, the first events on the pathway to the Grignard reagents involve a cascade of three (one intermolecular followed by two intramolecular) electron transfers. Introduction of a p-methoxy substituent on the phenyl ring, making the phenyl group a poorer electron acceptor, suppresses this specific second role. Applied to the mechanism of Grignard reagent formation, this p-methoxy effect is consistent with a triggering mechanistic act of electron transfer from the metal to the aryl halide rather than with a concerted oxidative addition. A similar change in selectivity is observed, when a p-methoxy group is introduced onto a phenyl group that also bears a halogen, but its origin is different: this effect is associated with the shortening of the lifetime of the radical anion formed by the triggering electron transfer. These observations reemphasise our earlier proposals to use concepts originating from, electrochemical kinetics to explain, the selectivities of reactions occurring at metal/solution interfaces. This conjecture could possibly hold for any interface where the diffusion of reactive species plays a role in the settling of selectivity. These concepts emphasise the necessity to consider, for each reactive species, their average distance of diffusion away from the metal/solution interface. Wiley-VCH Verlag GmbH & Co. KGaA.
Formation of Grignard reagents from aryl halides: Effective radical probes hint at a nonparticipation of dianions in the mechanism
Bodineau, Nicolas,Mattalia, Jean-Marc,Thimokhin, Vitaliy,Handoo, Kishan,Négrel, Jean-Claude,Chanon, Michel
, p. 2303 - 2306 (2007/10/03)
(equation presented) We have prepared highly efficient radical probes 2a-b involving the hex-5-enyl rearrangement. The reaction of 2a-b with active magnesium leads to the cyclized products 4a-b, providing a direct evidence of radical intermediates during the formation of aryl Grignard reagents. The variations of yields for cyclized products 4a-b as a function of structural modifications in 2a-b suggest that the intervention of dianions is not necessary to explain the observed results.
