- Visible-light-mediated multicomponent reaction for secondary amine synthesis
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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.
- Wang, Xiaochen,Zhu, Binbing,Dong, Jianyang,Tian, Hao,Liu, Yuxiu,Song, Hongjian,Wang, Qingmin
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supporting information
p. 5028 - 5031
(2021/05/28)
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- Visible-Light-Mediated C-I Difluoroallylation with an α-Aminoalkyl Radical as a Mediator
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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.
- Yue, Fuyang,Dong, Jianyang,Liu, Yuxiu,Wang, Qingmin
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supporting information
p. 7306 - 7310
(2021/10/01)
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- Aliphatic C-H Bond Iodination by a N-Iodoamide and Isolation of an Elusive N-Amidyl Radical
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Contrary to C-H chlorination and bromination, the direct iodination of alkanes represents a great challenge. We reveal a new N-iodoamide that is capable of a direct and efficient C-H bond iodination of various cyclic and acyclic alkanes providing iodoalkanes in good yields. This is the first use of N-iodoamide for C-H bond iodination. The method also works well for benzylic C-H bonds, thereby constituting the missing version of the Wohl-Ziegler iodination reaction. Mechanistic details were elucidated by DFT computations, and the N-centered radical derived from the used N-iodoamide, which is the key intermediate in this process, was matrix-isolated in a solid argon matrix and characterized by UV-vis as well as IR spectroscopy.
- Artaryan, Alexander,Mardyukov, Artur,Kulbitski, Kseniya,Avigdori, Idan,Nisnevich, Gennady A.,Schreiner, Peter R.,Gandelman, Mark
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p. 7093 - 7100
(2017/07/26)
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- PROCESS FOR THE PREPARATION OF N-IODOAMIDES
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The present invention provides new stable crystalline N-iodoamides - 1-iodo- 3,5,5-trimethylhydantoin (1-ITMH) and 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO). The present invention further provides a process for the preparation of organic iodides using N-iodoamides of this invention and recovery of the amide co-products from waste water.
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Paragraph 00291-00292
(2015/05/26)
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- A structure-activity study of Ni-catalyzed alkyl-alkyl kumada coupling. Improved catalysts for coupling of secondary alkyl halides
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A structureactivity study was carried out for Ni catalyzed alkylalkyl Kumada-type cross coupling reactions. A series of new nickel(II) complexes including those with tridentate pincer bis(amino)amide ligands (RN2N) and those with bidentate mixed amino-amide ligands (RNN) were synthesized and structurally characterized. The coordination geometries of these complexes range from square planar, tetrahedral, to square pyramidal. The complexes had been examined as precatalysts for cross coupling of nonactivated alkyl halides, particularly secondary alkyl iodides, with alkyl Grignard reagents. Comparison was made to the results obtained with the previously reported Ni pincer complex [( MeN2N)NiCl]. A transmetalation site in the precatalysts is necessary for the catalysis. The coordination geometries and spin-states of the precatalysts have a small or no influence. The work led to the discovery of several well-defined Ni catalysts that are significantly more active and efficient than the pincer complex [(MeN2N)NiCl] for the coupling of secondary alkyl halides. The best two catalysts are [(HNN)Ni(PPh3)Cl] and [(HNN)Ni(2,4-lutidine)Cl]. The improved activity and efficiency was attributed to the fact that phosphine and lutidine ligands in these complexes can dissociate from the Ni center during catalysis. The activation of alkyl halides was shown to proceed via a radical mechanism.
- Ren, Peng,Vechorkin, Oleg,Von Allmen, Kim,Scopelliti, Rosario,Hu, Xile
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supporting information; experimental part
p. 7084 - 7095
(2011/06/26)
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- NaIO4-KI-NaN3 as a new reagent system for C-H functionalization in hydrocarbons
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The NaIO4-KI-NaN3 combination has been found to be an efficient, reliable, and inexpensive reagent system for mono- and 1,2-difunctionalization of hydrocarbons via C-H bond activation to afford vicinal azido- and acetoxy iodinations of cyclic hydrocarbons.
- Chouthaiwale, Pandurang V.,Suryavanshi, Gurunath,Sudalai, Arumugam
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scheme or table
p. 6401 - 6403
(2009/04/06)
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- Direct bromination and iodination of non-activated alkanes by hypohalite reagents
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The direct functionalisation of alkanes through bromination and iodination has been successfully achieved. The combination of stoichiometric mixtures of elemental halogen and sodium alkoxides leads to the formation of alkyl hypobromites and hypoiodites as reagents. The halogenation occurs without external photostimulation under thermal reaction conditions. Georg Thieme Verlag Stuttgart.
- Montoro, Raul,Wirth, Thomas
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p. 1473 - 1478
(2007/10/03)
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- New iodination reactions of saturated hydrocarbons
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Unactivated C-H bonds react with iodine when exposed to trimethylsilyl azide in the presence of a hypervalent iodine reagent or, alternatively, to aqueous H2O2, acetic anhydride, and sodium azide (see scheme). (Chemical Equation Presented).
- Barluenga, Jose,Campos-Gomez, Esther,Rodriguez, David,Gonzalez-Bobes, Francisco,Gonzalez, Jose M.
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p. 5851 - 5854
(2007/10/03)
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- Direct Iodination of Alkanes
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(Matrix presented) A cheap and efficient iodination of hydrocarbons can be achieved by generating tert-butyl hypoiodite from iodine and sodium tert-butoxide. The alkane is reactant and solvent, and this metal-free process provides a clean solution for their direct iodination.
- Montoro, Raul,Wirth, Thomas
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p. 4729 - 4731
(2007/10/03)
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- Monoetherification of tert-Butylated Pyrocatechols upon Irradiation of Their Solutions in Hydrocarbons
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Products of reactions of tert-butylated pyrocatechols with alkyl radicals were studied. The major products formed upon γ-irradiation of deaerated solutions of 4-tert-butyl- and 3,5-di-tert-butylpyrocatechol in hexane and cyclohexane are monoalkyl ethers, which were identified by NMR spectroscopy (1H, 13C, 1H-1H NOESY technique) and gas chromatography-mass spectrometry.
- Maslovskaya,Savchenko
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p. 394 - 400
(2007/10/03)
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- Activation of alkanes upon reaction with PhI(OAc)2-I2
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You can also choose from alkanes! Either mono- or bifunctional iodo derivatives can be prepared from alkanes (see scheme) in an efficient and selective manner by using PhI(OAc)2, I2, and an alcohol.
- Barluenga, Jose,Gonzalez-Bobes, Francisco,Gonzalez, Jose M.
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p. 2556 - 2558
(2007/10/03)
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- The first efficient iodination of unactivated aliphatic hydrocarbons
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No heavy metals, no enzymes, and a simple protocol: the direct iodination of aliphatic hydrocarbons, which has not been possible to date, can now be carried out in multiphase systems [see for example Eq. (l)]. In situ generated tetraiodomethane serves as a key intermediate in this selective radical chain reaction initiated by a single electron transfer. This room-temperature, efficient transformation is highly regioselective, easy to work-up, and hence widely applicable.
- Schreiner, Peter R.,Lauenstein, Oliver,Butova, Ekaterina D.,Fokin, Andrey A.
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p. 2786 - 2788
(2007/10/03)
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