Xn:Harmful;
75-30-9Relevant articles and documents
Quantitative reaction kinetics in the liquid state by in situ XAFS
Epple, Matthias,Troeger, Larc,Hilbrandt, Nicole
, p. 3035 - 3037 (1997)
By quantitative evaluation of in situ recorded Br K-edge XAFS spectra we obtained Kinetic parameters for the halogen exchange in 2-bromopropane with sodium iodide ('Finkelstein reaction'). The results compare well with the classical data by Ingold and co-workers. Thus, XAFS is a suitable method to quantitatively monitor reactions in the liquid state.
Photoinduced Palladium-Catalyzed Dicarbofunctionalization of Terminal Alkynes
Yang, Zhen,Koenigs, Rene M.
supporting information, p. 3694 - 3699 (2021/02/01)
Herein, a conceptually distinct approach was developed that allowed for the dicarbofunctionalization of alkynes at room temperature using simple, bench-stable alkyl iodides and a second molecule of alkyne as coupling partner. Specifically, the photochemical activation of palladium complexes enabled this strategic dicarbofunctionalization via addition of alkyl radicals from secondary and tertiary alkyl iodides and formation of an intermediate palladium vinyl complex that could undergo subsequent Sonogashira reaction with a second alkyne molecule. This alkylation–alkynylation sequence allowed the one-step synthesis of 1,3-enynes including heteroarenes and biologically active compounds with high efficiency without exogenous photosensitizers or oxidants and now opens up pathways towards cascade reactions via photochemical palladium catalysis.
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.
Ruthenium bipyridyl tethered porous organosilica: A versatile, durable and reusable heterogeneous photocatalyst
Jana, Avijit,Mondal, John,Borah, Parijat,Mondal, Sujan,Bhaumik, Asim,Zhao, Yanli
supporting information, p. 10746 - 10749 (2015/06/30)
A versatile heterogeneous photocatalysis protocol was developed by using ruthenium bipyridyl tethered porous organosilica (Ru-POS). The versatility of the Ru-POS catalyst in organo-photocatalysis was explored by (i) oxidative aromatization of Hantzsch ester, (ii) reductive dehalogenation of alkyl halides, and (iii) functional group interconversion (FGI) of alcohols to alkyl halides. This journal is
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.
Carbodeoxygenation of biomass: The carbonylation of glycerol and higher polyols to monocarboxylic acids
Coskun, Timur,Conifer, Christopher M.,Stevenson, Laura C.,Britovsek, George J. P.
supporting information, p. 6840 - 6844 (2013/07/05)
Glycerol is converted to a mixture of butyric and isobutyric acid by rhodium- or iridium-catalysed carbonylation using HI as the co-catalyst. The initial reaction of glycerol with HI results in several intermediates that lead to isopropyl iodide, which upon carbonylation forms butyric and isobutyric acid. At low HI concentration, the intermediate allyl iodide undergoes carbonylation to give vinyl acetic acid and crotonic acid. Higher polyols CnH n+2(OH)n are carbonylated to the corresponding C n+1 mono-carboxylic acids. Copyright
Sterically controlled alkylation of arenes through iridium-catalyzed C-H borylation
Robbins, Daniel W.,Hartwig, John F.
supporting information, p. 933 - 937 (2013/02/25)
Complementary chemistry: A one-pot method for the site-selective alkylation of arenes controlled by steric effects is reported. The process occurs through Ir-catalyzed C-H borylation, followed by Pd- or Ni-catalyzed coupling with alkyl electrophiles. This selectivity complements that of the typical Friedel-Crafts alkylation; meta-selective alkylation of a broad range of arenes with various electronic properties and functional groups occurs in good yield with high site selectivity. Copyright
Selective reduction of biomass by hydriodic acid and its in situ regeneration from iodine by metal/hydrogen
Yang, Weiran,Grochowski, Matthew R.,Sen, Ayusman
scheme or table, p. 1218 - 1222 (2012/09/08)
HI returns: Hydroiodic acid is a highly selective reducing reagent for a wide variety of substrates. Its application is limited by the formation of iodine and the difficulty in reconverting that iodione back to HI in situ. We report the facile conversion of I2 to HI by metal-catalyzed hydrogenation in the presence of water, and demonstrate the utility of this process in the conversion of fructose to 5-methyfurfural and glycerol to 2-iodopropane. Copyright
Nickel-catalyzed Negishi cross-couplings of secondary nucleophiles with secondary propargylic electrophiles at room temperature
Smith, Sean W.,Fu, Gregory C.
supporting information; experimental part, p. 9334 - 9336 (2009/05/16)
(Chemical Equation Presented) Mild thing: The first nickel-based catalysts for cross-couplings of secondary organometallic nucleophiles with secondary alkyl electrophiles have been developed. Thus, Negishi reactions proceed under mild conditions (at room temperature with no basic activators) in the presence of NiCl2·glyme and a tridentate ligand (see scheme).
