- Conversion of Aryl Aldehydes to Benzyl Iodides and Diarylmethanes by H3PO3/I2
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For the first time, H3PO3 was used as both the reducing reagent and the promotor in the reductive benzylation reactions with aryl aldehydes. By using a H3PO3/I2 combination, various aromatic aldehydes underwent iodination reactions and Friedel-Crafts type reactions with arenes via benzyl iodide intermediates, readily producing benzyl iodides and diarylmethanes in good yields. Intramolecular cyclization reactions also took place, giving the corresponding cyclic compounds. This new strategy features easy-handling, low-cost, and metal-free conditions.
- Lv, Fang,Xiao, Jing,Xiang, Junchun,Guo, Fengzhe,Tang, Zi-Long,Han, Li-Biao
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p. 3081 - 3088
(2021/02/01)
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- Preparation method of benzyl iodide and derivatives thereof
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The invention discloses a preparation method of benzyl iodide and derivatives thereof, which comprises the following steps: in a protective atmosphere, carrying out heating reaction on aryl aldehyde and iodine elementary substance in the presence of a solvent and phosphorous acid to obtain benzyl iodide and derivatives thereof. According to the method, cheap and green solid phosphorous acid is selected as a reduction reagent for reaction, elemental iodine is selected as an iodine source, the benzyl iodide and the derivatives thereof are efficiently prepared from the aryl aldehyde compounds which are simple and easy to obtain by a one-pot one-step method under mild conditions, and the method has the advantages of simplicity in operation, cheap and easily available reagents, environmental friendliness and the like; and the use of expensive silicon-hydrogen compounds and transition metal catalysts is avoided, and the yield can reach 94% at most, so that the method is beneficial to industrial production.
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Paragraph 0053-0056
(2021/05/01)
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- Iminophosphorane-mediated regioselective umpolung alkylation reaction of α-iminoesters
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Umpolung reactions of imines, especially the asymmetric reactions, have been extensively studied as they provide access to important chiral amines in an efficient manner. The reactions studied range from simple Michael reactions to several kinds of other reactions such as the aza-benzoin reaction, aza-Stetter reaction, addition with MBH carbonate, and Ir-catalysed allylation. Herein, we report the first umpolung alkylation reaction of α-iminoesters with alkyl halides mediated by iminophosphorane as an organic superbase. The desired products were obtained in up to 82% yield with almost perfect regioselectivities. The key to the regioselectivity of this reaction was the use of 4-trifluoromethyl benzyl imines as a substrate. The products were successfully derivatised into the more functionalised molecules in good yields.
- Kukita, Mayu,Mino, Takashi,Omori, Kazuki,Sakamoto, Masami,Yoshida, Yasushi
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p. 4551 - 4564
(2021/05/31)
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- Cuprous complex containing diphospho-ortho-carborane ligand as well as preparation method and application thereof (by machine translation)
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The method comprises the following steps, adding :1) solution to the ortho-carborane solution n - BuLi, reacting, at room temperature for 30 - 60min;2), adding, and reacting 1 - 3h;3) with high yield CuI, of the monovalent copper complex to react alcohol and iodide to synthesize the iodo-hydrocarbon 3 - 6h, and synthesizing the iodo-hydrocarbon; through post-treatment at room temperature for synthesizing the iodo-copper complex, by the following steps: reacting the alcohol with the iodide at room temperature and carrying out post-treatment to obtain the monovalent copper complex . The preparation method comprises the following steps: catalyzing alcohol and iodide to react with the iodide, to synthesize the iodo- hydrocarbyl complex; and the method comprises the following steps: catalyzing alcohol and iodide to react. (by machine translation)
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Paragraph 0047-0049; 0052-0056
(2020/05/02)
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- Preparation method of benzyl iodide and derivatives thereof
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The invention discloses a preparation method of benzyl iodide and derivatives thereof. The preparation method comprises the following steps: under the reduction action of sodium borohydride, a benzylalcohol compound shown as a formula I reacts with elemental iodine to obtain benzyl iodide shown as a formula II and derivatives thereof; in the formula I and the formula II, R represents one or moresubstituents on a benzene ring and is selected from at least one of aryl, substituted or unsubstituted alkyl, halogen and nitro. The preparation method of benzyl iodide and derivatives thereof is scientific and reasonable, sodium borohydride which is mild in reactivity, low in price and easily available is used as a reducing agent, and elemental iodine is convenient and easily available; in addition, the preparation method has the characteristics of simplicity and convenience in operation, high synthesis yield, easiness in product purification, environmental friendliness and the like.
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Paragraph 0083-0087
(2020/06/09)
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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 00282-00283
(2015/05/26)
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- Highly enantioselective copper-catalyzed alkylation of β-ketoesters and subsequent cyclization to spirolactones/bi-spirolactones
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Cu-catalyzed enantioselective alkylation of β-ketoesters using alcohols for in situ preparation of alkylating reagents is reported. A number of functionalized β-ketoesters containing a quaternary carbon stereocenter are obtained with up to 99% ee. The alkylation products derived from 2-substituted allylic alcohols or their corresponding iodides can then be converted to spirolactones, bi-spirolactones, and related chiral target products.
- Deng, Qing-Hai,Wadepohl, Hubert,Gade, Lutz H.
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supporting information; experimental part
p. 2946 - 2949
(2012/03/26)
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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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- Convenient and efficient method for the iodination of benzylic and aliphatic alcohols by using Al(HSO4)3/KI in nonaqueous solution
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A simple and efficient method for the iodination of benzylic and aliphatic alcohols by using Al(HSO4)3/KI in n-hexane as solvent is reported. Mild reaction conditions and good to excellent yields of the products are the noteworthy advantages of the method. Copyright Taylor & Francis LLC.
- Tajik, Hassan,Shirini, Farhad,Zolfigol, Mohammad Ali,Samimi, Faeze
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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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- HOMOLYTIC DISPLACEMENT AT CARBON. X. TOLUENESULPHONYL IODIDE AS A SOURCE OF TOLUENESULPHONYL RADICALS FOR THE FORMATION OF ALLYL-, BENZYL-, CYCLOPROPYLCARBINYL-, SPIROCYCLOPROPYLCYCLOALKYL-, BICYCLOALKYL-, AND BICYCLOALKYL-4-TOLYLSULPHONES FROM ORGANOCOBALOXIMES
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4-Toluenesulphonyl iodide reacts thermally at alkylsulphone.Spiro- and bicyclo-alkyl compounds are also formed with other free radical precursors.The reactions are believed to take place through a chain mechanism in which cobaloxime(II), present adventitiously or formed by partial homolysis of the substrate, abstracts iodine from the toluenesulphonyl iodide to give the toluenesulphonyl radical, which attacks the organic ligand of the cobaloxime, preferably at the terminal olefinic carbon, thereby displacing cobaloxime(II) and giving the observed organic product.
- Ashcroft, Martyn R.,Bougeard, Peter,Bury, Adrian,Cooksey, Christopher J.,Johnson, Michael D.
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p. 403 - 416
(2007/10/02)
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- α-NITRO SULFONES. 2. CONVENIENT NEW SYNTHESIS AND SELECTED FUNCTIONAL GROUP TRANSFORMATIONS
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(Phenylsulfonyl)nitromethane (1) is preferentially C-alkylated by benzylic halides and primary alkyl iodides, affording secondary α-nitro sulfone products. α-Nitro sulfones are also obtained from the corresponding C-alkylation of allylic acetates in the presence of catalytic tetrakis(triphenylphosphine)palladium.The palladium(0)-catalyzed reaction is stereospecific for geranyl and neryl acetates and is also regioselective.Desulfonation of α-nitro sulfones is readily accomplished by light-induced reduction with 1-benzyl-1,4-dihydronicotinamide (BNAH).Reduction of secondary α-nitro sulfones with 20percent aqueous titanium(III) chloride affords nitriles.Oxidation with alkaline permanganate affords carboxylic acids.
- Wade, Peter A.,Hinney, Harry R.,Amin, Nayan V.,Vail, Peter D.,Morrow, Scott D.,et al.
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p. 765 - 770
(2007/10/02)
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