542-69-8Relevant articles and documents
MeLi + LiCl in THF: One Heterodimer and no tetramers
Lecachey, Baptiste,Oulyadi, Hassan,Lameiras, Pedro,Harrison-Marchand, Anne,Gerard, Helene,Maddaluno, Jacques
, p. 5976 - 5983 (2010)
The structure of the aggregates formed when mixing methyllithium and lithium chloride in THF has been studied by multinuclear magnetic resonance at 170 K. The data suggest that only one new entity is observed, that is the dimer [(MeLi)(LiCl)], in equilibrium (K ≈ 0.6) with [MeLi]4 and [LiCl]2. NMR diffusion measurements lead to the conclusion that this dimer is trisolvated in THF at 170 K, a solvation scheme in agreement with DFT computations.
Reaction of Halide Ion with 2-(Phenylthio)ethyl Halides in Acetone
McManus, Samuel P.,Karaman, Rashid M.,Sedaghat-Herati, Reza,Harris, J. Milton
, p. 4764 - 4766 (1995)
2-(Phenylthio)ethyl chloride specifically deuterated α to the sulfur atom (i.e. 2-Cl) was employed to study the mechanism of displacement of chloride ion by iodide ion in dry acetone solution.Experimental evidence including rate studies has been accumulated that allows the conclusion to be drawn that iodide ion displaces chloride ion from 2-Cl by a classical SN2 mechanism to give 2-I.Under the reaction conditions, however, 2-I is reactive toward anchimerically-assisted ionization which leads to product with the deuterium label scrambled.Reaction of 2-Cl with bromide ion follows a similar course.Our displacement reactions of halide ions by halide ions showed the expected nucleophilicity order of Cl(1-) > Br(1-) > I(1-) and the normal leaving group order of I(1-) > Br(1-) > Cl(1-).An interesting counterion effect was noted with iodides displacing chloride ion.While potassium iodide in acetone converted 2-Cl to the mixture of iodides 2-I and 3-I, tetrabutylammonium iodide caused conversion but the products reverted completely back to the label-scrambled chlorides.The difference in these results is probably because of differences in the thermodynamics of the two systems.
Visible-light-mediated multicomponent reaction for secondary amine synthesis
Wang, Xiaochen,Zhu, Binbing,Dong, Jianyang,Tian, Hao,Liu, Yuxiu,Song, Hongjian,Wang, Qingmin
supporting information, p. 5028 - 5031 (2021/05/28)
The widespread presence of secondary amines in agrochemicals, pharmaceuticals, natural products, and small-molecule biological probes has inspired efforts to streamline the synthesis of molecules with this functional group. Herein, we report an operationally simple, mild protocol for the synthesis of secondary amines by three-component alkylation reactions of imines (generated in situ by condensation of benzaldehydes and anilines) with unactivated alkyl iodides catalyzed by inexpensive and readily available Mn2(CO)10. This protocol, which is compatible with a wide array of sensitive functional groups and does not require a large excess of the alkylating reagent, is a versatile, flexible tool for the synthesis of secondary amines.
Visible-Light-Mediated C-I Difluoroallylation with an α-Aminoalkyl Radical as a Mediator
Yue, Fuyang,Dong, Jianyang,Liu, Yuxiu,Wang, Qingmin
supporting information, p. 7306 - 7310 (2021/10/01)
Herein, we report a protocol for direct visible-light-mediated C-I difluoroallylation reactions of α-trifluoromethyl arylalkenes with alkyl iodides at room temperature with an α-aminoalkyl radical as a mediator. The protocol permits efficient functionalization of various α-trifluoromethyl arylalkenes with cyclic and acyclic primary, secondary, and tertiary alkyl iodides and is scalable to the gram level. This mild protocol uses an inexpensive mediator and is suitable for late-stage functionalization of complex natural products and drugs.
Scalable and Phosphine-Free Conversion of Alcohols to Carbon-Heteroatom Bonds through the Blue Light-Promoted Iodination Reaction
Liu, Bin,Elder, W. Zachary,Miyake, Garret M.
, p. 3717 - 3727 (2020/03/04)
One of the fundamental and highly valuable transformations in organic chemistry is the nucleophilic substitution of alcohols. Traditionally, these reactions require strategies that employ stoichiometric hazardous reagents and are associated with difficulty in purification of the by-products. To overcome these challenges, here, we report a simple route toward the diverse conversion of alcohols via an SN2 pathway, in which blue light-promoted iodination is used to form alkyl iodide intermediates from simple unreactive alcohols. The scope of the process tolerates a range of nucleophiles to construct C-N, C-O, C-S, and C-C bonds. Furthermore, we also demonstrate that this method can be used for the preparation and late-stage functionalization of pharmaceuticals, as highlighted by the syntheses of thiocarlide, butoxycaine, and pramoxine.
Halogen-Imparted Reactivity in Lithium Carbenoid Mediated Homologations of Imine Surrogates: Direct Assembly of bis-Trifluoromethyl-β-Diketiminates and the Dual Role of LiCH2I
Castoldi, Laura,Holzer, Wolfgang,Ielo, Laura,Lombino, Jessica,Pace, Vittorio,Prandi, Cristina,Roller, Alexander,Touqeer, Saad
supporting information, p. 20852 - 20857 (2020/09/12)
The selective formal insertion (homologation) of a carbon unit bridging the two trifluoroacetamidoyl chlorides (TFAICs) units is reported. The tactic is levered on a highly chemoselective homologation–metalation–acyl nucleophilic substitution sequence which precisely enables to assemble novel trifluoromethylated β-diketiminates within a single synthetic operation. Unlike previous homologations conducted with LiCH2Cl furnishing aziridines, herein we exploit the unique capability of iodomethyllithium to act contemporaneously as a C1 source (homologating effect) and metalating agent. The mechanistic rationale grounded on experimental evidences supports the hypothesized proposal and, the structural analysis gathers key aspects of this class of valuable ligands in catalysis.
Visible-Light-Promoted Remote C-H Functionalization of o-Diazoniaphenyl Alkyl Sulfones
Du, Shaofu,Kimball, Elizabeth Ann,Ragains, Justin R.
supporting information, p. 5553 - 5556 (2017/10/25)
Visible-light irradiation of ortho-diazoniaphenyl alkyl sulfones in the presence of Ru(bpy)32+ results in remote Csp3-H functionalization. Key mechanistic steps in these processes involve intramolecular hydrogen atom transfer from Csp3-H bonds to aryl radicals to generate alkyl/benzyl radicals. Subsequent polar crossover occurs by single-electron oxidation of the alkyl/benzyl radicals to carbenium ions that then intercept nucleophiles. We have developed remote hydroxylations, etherifications, an amidation, and C-C bond formation processes using this strategy.
HALIDE-MEDIATED DEALKYLATION OF PHOSPHOTRIESTERS
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Paragraph 0010; 0012; 0051, (2018/02/03)
In one embodiment, a method includes contacting a phosphotriester and a halogen salt in a polar solvent. In another embodiment, a method for dealkylating tributylphosphate includes contacting tributylphosphate and a halogen salt in a polar solvent.
A transition-metal-free Heck-type reaction between alkenes and alkyl iodides enabled by light in water
Liu, Wenbo,Li, Lu,Chen, Zhengwang,Li, Chao-Jun
supporting information, p. 6170 - 6174 (2015/06/08)
A transition-metal-free coupling protocol between various alkenes and non-activated alkyl iodides has been developed by using photoenergy in water for the first time. Under UV irradiation and basic aqueous conditions, various alkenes efficiently couple with a wide range of non-activated alkyl iodides. A tentative mechanism, which involves an atom transfer radical addition process, for the coupling is proposed.
Microwave assisted synthesis of spirocyclic pyrrolidines - σ1 receptor ligands with modified benzene-N-distance
Jasper, Annemarie,Schepmann, Dirk,Lehmkuhl, Kirstin,Vela, Jose Miguel,Buschmann, Helmut,Holenz, Joerg,Wuensch, Bernhard
experimental part, p. 327 - 336 (2012/08/13)
Two series of σ1 ligands with a spiro[[2]benzopyran-1, 3′-pyrrolidine] (3) and a spiro[[2]benzofuran-1,3′-pyrrolidine] (4) framework were synthesized and pharmacologically evaluated. Several reaction steps were considerably improved by microwave irradiation. The σ1 affinity of the spirocyclic ligands correlates nicely with the benzene-N-distance, i.e. 2 1 affinity of both compound classes could be increased with large N-substituents (e.g. 2-phenylethyl, octyl). Nevertheless the benzyl derivative 4a represents the most promising σ1 ligand (Ki = 25 nM) due to its high selectivity against the σ2 subtype (>40-fold), the NMDA receptor and 5-HT6 and 5-HT7 receptors. Moreover, 4a did not inhibit the hERG channel in the heart.
