- Iron-Catalyzed Oxyalkylation of Terminal Alkynes with Alkyl Iodides
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A general oxyalkylation of terminal alkynes enabled by iron catalysis has been developed. Primary and secondary alkyl iodides acted as the alkylating reagents and afforded a range of α-alkylated ketones under mild reaction conditions. Acetyl tert-butyl peroxide (TBPA) was used as the radical relay precursor, providing the initiated methyl radical to start the radical relay process. Preliminary mechanistic studies were conducted, and late-stage functionalizations of natural product derivatives were performed.
- Deng, Weili,Ye, Changqing,Li, Yajun,Li, Daliang,Bao, Hongli
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supporting information
p. 261 - 265
(2019/01/10)
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- Ready access to organoiodides: Practical hydroiodination and double-iodination of carbon-carbon unsaturated bonds with I2
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By using I2 or I2/H3PO3 system, various alkenes and alkynes were converted to the corresponding alkyl and alkenyl iodides in good yields. In the presence of I2, alkynes could be di-iodinated using H2O as the solvent in air at room temperature. This method also features the simple work-up procedure since the pure product could be obtained by extraction. Additionally, for the first time, combining with the non-toxic and cheap phosphonic acid H3PO3, alkenes and alkynes were also hydroiodinated successfully, which provides a simple and practical approach for synthesis of organoiodides.
- Xiao, Jing,Han, Li-Biao
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p. 3510 - 3515
(2019/05/17)
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- Method of preparing iodine alkane by using rhodium catalysis
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The invention relates to the field of organic synthesis and discloses a synthetic method of iodine alkane. The synthetic method of the iodine alkane, disclosed by the invention, comprises the following steps: taking olefin as a starting raw material, adding a rhodium metal catalyst, a phosphine ligand, a solvent and molecular iodine into a pressurizing reaction kettle, introducing hydrogen and then synthesizing a series of the iodine alkane by using one-step reaction. The reaction temperature is 0 to 60 DEG C, the molar ratio of the rhodium metal to the olefin is (0.00001 to 1) to (0.1 to 1) and the molar ratio of the iodine to the olefin is (0.5 to 1) to (10 to 1). The synthetic method of the iodine alkane, disclosed by the invention, has obvious advantages of wide application range, short process flow and low cost of the raw materials; the synthetic method of the iodine alkane is suitable for industrialized production of a series of the iodine alkanes.
- -
-
Paragraph 0040-0041
(2018/04/03)
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- Rhodium-Catalyzed Generation of Anhydrous Hydrogen Iodide: An Effective Method for the Preparation of Iodoalkanes
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The preparation of anhydrous hydrogen iodide directly from molecular hydrogen and iodine using a rhodium catalyst is reported for the first time. The anhydrous hydrogen iodide generated was proven to be highly active in the transformations of alkenes, phenyl aldehydes, alcohols, and cyclic ethers to the corresponding iodoalkanes. Therefore, the present methodology not only has provided convenient access to anhydrous hydrogen iodide but also offers a practical preparation method for various iodoalkanes in excellent atom economy.
- Zeng, Chaoyuan,Shen, Guoli,Yang, Fan,Chen, Jingchao,Zhang, Xuexin,Gu, Cuiping,Zhou, Yongyun,Fan, Baomin
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supporting information
p. 6859 - 6862
(2018/10/25)
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- Palladium and visible-light mediated carbonylative Suzuki-Miyaura coupling of unactivated alkyl halides and aryl boronic acids
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Herein, a simple and efficient method for the palladium-catalyzed carbonylation of aryl boronic acids with unactivated alkyl iodides and bromides under visible-light irradiation, ambient temperature and low CO-pressure is presented. Notably, the procedure uses readily available equipment and an inexpensive palladium catalyst to generate the key alkyl radical intermediate. These mild conditions enabled the synthesis of a range of functionalized aryl alkyl ketones including the antipsychotic drug, melperone.
- Roslin, Sara,Odell, Luke R.
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supporting information
p. 6895 - 6898
(2017/07/10)
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- Method for the Preparation of Iodoalkanes
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The present invention relates to an atom economic procedure of preparing iodoalkanes by hydroiodination of alkenes. In particular the present method features the generation of anhydrous hydrogen iodide from atomic hydrogen and iodine in situ by using transition metal precursor and phosphine ligandcatalyst.
- -
-
Paragraph 0036
(2017/08/07)
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- A mild method for the replacement of a hydroxyl group by halogen. 1. Scope and chemoselectivity
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α-Chloro-, bromo- and iodoenamines, which are readily prepared from the corresponding isobutyramides have been found to be excellent reagents for the transformation of a wide variety of alcohols or carboxylic acids into the corresponding halides. Yields are high and conditions are very mild thus allowing for the presence of sensitive functional groups. The reagents can be easily tuned allowing therefore the selective monohalogenation of polyhydroxylated molecules. The scope and chemoselectivity of the reactions have been studied and reaction mechanisms have been proposed.
- Munyemana, Fran?ois,George, Isabelle,Devos, Alain,Colens, Alain,Badarau, Eduard,Frisque-Hesbain, Anne-Marie,Loudet, Aurore,Differding, Edmond,Damien, Jean-Marie,Rémion, Jeanine,Van Uytbergen, Jacqueline,Ghosez, Léon
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p. 420 - 430
(2015/12/31)
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- An efficient and selective method for the iodination and bromination of alcohols under mild conditions
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A straightforward and effective procedure for the conversion of a variety of alcohols into the corresponding alkyl iodides and bromides is described using KX/P2O5 (X = I, Br). The reactions were easily carried out in acetonitrile under mild conditions. Using this method, the selective conversion of benzylic alcohols in the presence of aliphatic alcohols was achieved.
- Khazdooz, Leila,Zarei, Amin,Aghaei, Hamidreza,Azizi, Ghobad,Gheisari, Mohammad Mehdi
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p. 168 - 171
(2015/12/30)
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- Application of "click" chemistry in solid phase synthesis of alkyl halides
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A convenient and highly selective microwave assisted procedure for the conversion of allylic, benzylic and aliphatic alcohols to their corresponding halides using polymer-bound triphenylphosphine and iodine is presented. In case of symmetrical diols, mono-iodination product is obtained in very high yield. Additionally, highly regioselective behavior is observed in our procedure. Simplicity in operation, no column chromatography required for the purification of the products, recyclability of the reagents used, short reaction times and good to excellent yields are the advantages of our protocol. Most functional groups remain unaffected under our reaction condition.
- Das, Diparjun,Chanda, Tridib,Rokhum, Lalthazuala
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p. 775 - 783
(2016/01/20)
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- Solvent-free, microwave-assisted conversion of tosylates into iodides
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A highly efficient method for the conversion of primary tosylates into the corresponding iodides is outlined. The method involves heating a neat mixture of the tosylate and solid sodium iodide in a microwave cavity. Reaction times are short, usually about 60 minutes, delivering high yields. This procedure is especially useful for the in situ generation of volatile primary iodides, and for most of the primary iodides, the crude product is sufficiently pure.
- Cao, Jia,Perlmutter, Patrick
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p. 1360 - 1361
(2014/11/07)
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- A facile and green protocol for nucleophilic substitution reactions of sulfonate esters by recyclable ionic liquids [bmim][X]
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Ionic liquids [bmim][X] (X = Cl, Br, I, OAc, SCN) are highly efficient reagents for nucleophilic substitution reactions of sulfonate esters derived from primary and secondary alcohols. The counter anions (X-) of the ionic liquids, [bmim][X], effectively replace the sufonates affording the corresponding substitution products such as alkyl halides, acetates, and thiocyanides in excellent yields. The newly developed protocol is very environmentally attractive because the reactions use stoichiometric amounts of ionic liquids as sole reagents in most cases and do not require additional solvents, any other activating reagents, non-conventional equipment, or special precautions. Moreover, these ionic liquids can be readily recycled without loss of reactivity, making the whole process greener.
- Liu, Yajun,Xu, Yongnan,Jung, Sun Ho,Chae, Junghyun
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p. 2692 - 2698,7
(2012/12/12)
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- A facile and green protocol for nucleophilic substitution reactions of sulfonate esters by recyclable ionic liquids [bmim][X]
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Ionic liquids [bmim][X] (X = Cl, Br, I, OAc, SCN) are highly efficient reagents for nucleophilic substitution reactions of sulfonate esters derived from primary and secondary alcohols. The counter anions (X-) of the ionic liquids, [bmim][X], effectively replace the sufonates affording the corresponding substitution products such as alkyl halides, acetates, and thiocyanides in excellent yields. The newly developed protocol is very environmentally attractive because the reactions use stoichiometric amounts of ionic liquids as sole reagents in most cases and do not require additional solvents, any other activating reagents, non-conventional equipment, or special precautions. Moreover, these ionic liquids can be readily recycled without loss of reactivity, making the whole process greener. Georg Thieme Verlag KG Stuttgart · New York.
- Liu, Yajun,Xu, Yongnan,Jung, Sun Ho,Chae, Junghyun
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p. 2692 - 2698
(2013/01/15)
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- Highly regioselective hydroiodination of terminal alkynes and silylalkynes with iodine and phosphorus reagents leading to internal iodoalkenes
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Markovnikov-type hydroiodination of terminal alkynes with iodine and Ph2P(O)H took place selectively to afford the corresponding internal iodoalkenes in good yields. Combination of (PhO)2P(O)H and Ph 2P(O)OH instead of Ph2P(O)H also provided internal iodoalkenes in excellent yields. This hydroiodination is advantageous in terms of mild conditions, convenient operation, and tolerance to various functional groups. In addition, direct synthesis of internal iodoalkenes from silylalkynes was also achieved by using a mixed system of iodine and phosphorus reagents.
- Kawaguchi, Shin-Ichi,Masuno, Haruna,Sonoda, Motohiro,Nomoto, Akihiro,Ogawa, Akiya
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p. 9818 - 9825
(2012/11/07)
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- Efficient organic transformations mediated by ZrOCl28H 2O in Water
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Operationally simple and environmentally benign methods for some organic transformations comprising reductive coupling of sulfonyl chlorides, chemoselective deoxygenation of sulfoxides, and halogenation of alcohols mediated by ZrOCl28H2O/MX in water have been developed.
- Jafarpour, Maasoumeh,Rezaeifard, Abdolreza,Heidari, Mahdieh
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experimental part
p. 1470 - 1482
(2011/10/05)
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- Highly selective hydroiodation of alkynes using an iodine-hydrophosphine binary system
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Figure presented A novel hydroiodation of alkynes (1) using an iodine/hydrophosphine binary system takes place regioselectively to provide the corresponding Markovnikov-type adducts (2) in good yield. This hydroiodation is advantageous in terms of mild conditions, convenient operation, and tolerance to various functional groups.
- Kawaguchi, Shin-Ichi,Ogawa, Akiya
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supporting information; experimental part
p. 1893 - 1895
(2010/06/21)
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- Selective conversion of alcohols into alkyl iodides using a thioiminium salt
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(Chemical Equation Presented) Treatment of a range of primary and secondary alcohols with MeSCH=NMe2+ I- affords the corresponding alkyl iodides in excellent yield with straightforward purification. Selective formation of a primary iodide in the presence of a secondary alcohol can be achieved.
- Ellwood, Adam R.,Porter, Michael J.
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supporting information; body text
p. 7982 - 7985
(2010/02/28)
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- An efficient and facile hydroiodination of alkenes and alkynes PI using polymethylhydrosiloxane-iodine system
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A mild and efficient method has been developed for the synthesis of alkyl and alkenyl iodides from alkenes and alkynes using polymethylhydrosiloxane (PMHS) and iodine in chloroform at room temperature. The reagent system generates hydrogen iodide which regioselectively adds to the alkenes and alkynes. Copyright
- Das, Biswanath,Srinivas, Yallamalla,Holla, Harish,Narender, Ravirala
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p. 800 - 801
(2008/02/09)
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- Conversion of (sp3)C-F bonds of alkyl fluorides to (sp 3)C-heteroatom (heteroatom = I, SR, SeR, TeR) bonds by the use of magnesium reagents having heteroatom substituents
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A convenient method for conversion of (sp3)C-F bonds to (sp 3)C-Z (Z = I, SR, SeR, TeR) bonds has been developed. The reaction proceeds at room temperature using magnesium salts (Z-MgX). SN2 mechanism for substitiution of primary alkyl fluorides with MgI2 in ether was supported by the inversion of the stereochemistry of the carbon connecting to F. Copyright
- Begum, Shameem Ara,Terao, Jun,Kambe, Nobuaki
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p. 196 - 197
(2008/02/03)
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- 4-Aminophenyldiphenylphosphinite (APDPP), a new heterogeneous and acid scavenger phosphinite - Conversion of alcohols, trimethylsilyl, and tetrahydropyranyl ethers to alkyl halides with halogens or N-halosuccinimides
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A new heterogeneous phosphinite, 4-aminophenyldiphenylphosphinite (APDPP), is prepared and used for the efficient conversion of alcohols, trimethylsilyl ethers, and tetrahydropyranyl ethers to their corresponding bromides, iodides, and chlorides in the presence of molecular halogens or N-halosuccinimides. The amino group in this phosphinite acts as an acid scavenger and removes the produced acid. A simple filtration easily removes the phosphinate by-product.
- Iranpoor, Nasser,Firouzabadi, Habib,Gholinejad, Mohammad
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p. 1006 - 1012
(2007/10/03)
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- Facile conversion of alcohols into their bromides and iodides by N-bromo and N-iodosaccharins/triphenylphosphine under neutral conditions
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N-Bromo and N-iodosaccharins in the presence of triphenylphosphine convert alcohols into the corresponding bromides and iodides in good to excellent yields at room temperature under neutral conditions.
- Firouzabadi, Habib,Iranpoor, Nasser,Ebrahimzadeh, Farzaneh
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p. 1771 - 1775
(2007/10/03)
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- Silicaphosphine (Silphos): A filterable reagent for the conversion of alcohols and thiols to alkyl bromides and iodides
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Silicaphosphine (Silphos), [P(Cl)3-n(SiO2) n], as a new heterogeneous reagent is introduced. This reagent converts alcohols and thiols to their corresponding bromides and iodides in the presence of X2 (X=Br, I) in refluxing CH3CN in high to quantitative yields. Use of Silphos provides a highly practical method for the easy separation of the Silphos oxide byproduct by a simple filtration.
- Iranpoor, Nasser,Firouzabadi, Habib,Jamalian, Arezu,Kazemi, Foad
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p. 5699 - 5704
(2007/10/03)
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- A simple, efficient, and highly selective method for the iodination of alcohols using ZrCl4/NaI
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Iodination of primary, secondary, allylic, and benzylic alcohols giving their corresponding iodides was achieved with ZrCl4/NaI in anhydrous CH3CN with excellent yields and selectivities.
- Firouzabadi, Habib,Iranpoor, Nasser,Jafarpour, Maasoumeh
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p. 7451 - 7454
(2007/10/03)
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- A comparative kinetic study of nucleophilic substitution under PTC conditions in liquid-liquid and solid-liquid systems
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The phenomenon of initial exponential burst (IB) on kinetic curves in the reaction with solid salts was observed in the study on the S(N)2 substitution reaction of 2-octylmesylate with potassium halides under phase- transfer catalysis (PTC) conditions in liquid-liquid (l/l) and solid-liquid (s/l) systems. The mechanistic scheme describing the IB phenomenon in application to s/l PTC has been developed from the analysis of IB kinetic model known in enzyme kinetics.
- Yufit, Sergei S.,Zinovyev, Sergei S.
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p. 6319 - 6328
(2007/10/03)
-
- Finkelstein Reaction with Aqueous Hydrogen Halides Efficiently Catalysed by Lipophilic Quarternary Onium Salts
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The rate of halogen metathesis between halogenoalkanes RX 1-4 (X = F, Cl, Br, I) and aqueous concentrated hydrogen halides HY (Y = Cl, Br, I) is strongly accelerated under phase-transfer catalysis conditions, without solvent.The amount and nature of the nucleophilic species in the organic phase were determined.
- Landini, Dario,Albanese, Domenico,Mottadelli, Sabrina,Penso, Michele
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p. 2309 - 2312
(2007/10/02)
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- Single Electron Transfer Mechanism in the Reaction of 1,3-Dithianyllithium and Alkyl Iodides
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The reaction between 2-lithio-1,3-dithiane and optically active (R)-2-iodooctane was found to proceed with complete inversion of configuration.This result suggests that the SN2 (rather than single electron transfer (SET)) mechanism is the preferred pathway for reaction between dithianyllithium and unhindered alkyl halides.When the neopentyl-type radical probe 5,5-dimethyl-6-iodo-1-hexene was used as the substrate halide, 6-11percent cyclized alkylated product was obtained.This result suggests that when the SN2 pathway is blocked, SET mechanisms become operative to some extent, at least with iodide as the halogen.The reaction of dithianyllithium and (R)-2-iodooctane and 5,5-dimethyl-6-iodo-1-hexene, with hexane as the solvent, proceeds under heterogeneous conditions to bring about complete racemization of the respective iodide.These results demonstrate for the first time that 2-lithio-1,3-dithiane can act as electron donor in reactions initiated by electron transfer to alkyl iodides.
- Juaristi, Eusebio,Jimenez-Vazquez, Hugo A.
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p. 1623 - 1630
(2007/10/02)
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- SYNTHESIS OF ALKYL HALIDES UNDER NEUTRAL CONDITIONS
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Primary and secondary alcohols are efficiently converted to the corresponding alkyl halides under neutral conditions.
- Munyemana, Francois,Frisque-Hesbain, Anne-Marie,Devos, Alain,Ghosez, Leon
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p. 3077 - 3080
(2007/10/02)
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- A Facile Synthesis of Alkyl Iodides and Deuterated Alkyl Iodides by Hydroiodination and Deuterioiodination of Olefins
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Chlorotrimethylsilane/sodium iodide in the presence of water has been found as facile method for the hydroiodination of olefins to alkyl iodides under mild conditions.This procedure has successfully been extended to the preparation of deuterated alkyl iodides by using deuterium oxide in place of water.
- Irifune, Shinji,Kibayashi, Takao,Ishii, Yasutaka,Ogawa, Masaya
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p. 366 - 369
(2007/10/02)
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- A CONVENIENT METHOD FOR THE ADDITION OF HI TO UNSATURATED HYDROCARBONS USING I2 ON Al2O3
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Iodine reacts, under mild conditions, with hydroxyl groups on the surface of alumina to form HI which readily adds to unsaturated hydrocarbons to form alkyl and vinyl iodides.
- Stewart, Lyman J.,Gray, Donna,Pagni, Richard M.,Kabalka, George W.
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p. 4497 - 4498
(2007/10/02)
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- 1,2-BIS (DIPHENYLPHOSPHINO)ETHANE TETRAHALIDE: A CONVENIENT REAGENT FOR THE CONVERSION OF ALCOHOLS TO THE CORRESPONDING HALIDES
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Efficient and rapid conversion under mild conditions of various alcohols and tetrahydro-2-pyranyl (THP) protected alcohols into the corresponding halide (Br or I) are described using the corresponding 1,2-bis (triphenylphosphino)ethane tetrahalide.Tert-butyldimethylsilyl ethers, esters and olefins are stable to these conditions.
- Schmidt, Steven P.,Brooks, Dee W.
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p. 767 - 768
(2007/10/02)
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- NEW PREPARATION OF ALKYL IODIDES FROM THE CORRESPONDING ALCOHOLS
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It is shown that alkyl iodides can be obtained from the corresponding alkyl α-chloroethyl carbonate and NaI or by direct reaction between the alcohol, α-chloroethyl chloroformate and NaI.
- Brunet, J. J.,Laurent, H.,Caubere, P.
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p. 5445 - 5446
(2007/10/02)
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- A NOVEL ZIRCONIUM-CATALYZED HYDROALUMINATION OF OLEFINS
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Sterically hindered trialkylalanes, such as triisobutylalane, react with olefins at or below room temperature under the influence of a catalytic amount of Cl2ZrCp2 to effect hydroalumination of the olefins.The reaction can tolerate certain hetero-functional groups, such as OH, SPh and Br, which tend to interfere with previously reported hydroalumination procedures.
- Negishi, Ei-ichi,Yoshida, Tadao
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p. 1501 - 1504
(2007/10/02)
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