- Phenylethynylcobalamin: A light-stable and thermolysis-resistant organometallic vitamin B12 derivative prepared by radical synthesis
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Don't take this antivitamin! 2-Phenylethynylcobalamin (see picture) was prepared in a newly developed radical reaction using cob(II)alamin and 1-iodo-2-phenylethyne. It has an exceptionally short organometallic bond and is a remarkably light-stable and he
- Ruetz, Markus,Salchner, Robert,Wurst, Klaus,Fedosov, Sergey,Kraeutler, Bernhard
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- Synthesis and crystal structure of new ?-bonded alkynylcobalt(III) complexes of 1,3-bis(diacetylmonoximeimino)propane
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?-Alkynyl Costa complexes can be readily synthesized from the trans diiodo-1,3-bis(diacetylmonoximeimino)propanecobalt complex 1 and alkynyl Grignard reagents 2a-d.The conversions are carried out under daylight irradiation and give the cobalt acetylides 3
- Giese, Bernd,Zehnder, Margareta,Neuburger, Markus,Trach, Frank
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- Reaction of methyl iodide with organylethynyl silatranylmethyl chalcogenides
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The reactivity of organylethynyl silatranylmethyl chalcogenides RC=CYCH2Si(OCH2CH2)3N (R = Ph, Me3Si; Y = S, Se, Te) in the reaction with methyl iodide depending on the nature of the chalcogen Y, the substituent R at the triple bond, and the reaction conditions was studied.
- Sorokin,Voronkov,Lopyrev
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- Facile Access to Triazole-Fused 3,1-Benzoxazines Enabled by Metal-Free Base-Promoted Intramolecular C-O Coupling
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A convenient approach to assemble 1,2,3-triazole-fused 4 H -3,1-benzoxazines has been developed. Diverse alcohol-tethered 5-iodotriazoles, readily accessible by a modified protocol of Cu-catalyzed (3+2)-cycloaddition, were utilized as precursors of the target fused heterocycles. The intramolecular C-O coupling proceeded efficiently under base-mediated transition-metal-free conditions, furnishing cyclization products in yields up to 96%. Suppression of the competing reductive cleavage of the C-I bond was achieved by the use of Na 2CO 3in acetonitrile at 100 °C. This practical and cost-effective procedure features a broad substrate scope and valuable functional group tolerance.
- Tatevosyan, Stepan S.,Kotovshchikov, Yury N.,Latyshev, Gennadij V.,Lukashev, Nikolay V.,Beletskaya, Irina P.
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supporting information
p. 369 - 377
(2021/10/21)
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- Synthesis method of 1-iodo-alkyne compound
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The invention discloses a synthetic method of a 1-iodo-alkyne compound. The preparation method comprises the following steps: in an aerobic environment, mixing terminal alkyne, soluble inorganic iodized salt, sodium phenylsulfinate or a derivative thereof
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Paragraph 0036-0039
(2021/01/24)
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- Method for preparing 1-halogenated alkyne under catalysis of heterogeneous Ag catalyst at room temperature
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The invention discloses a novel method for preparing 1-halogenated alkyne under the catalysis of a heterogeneous Ag catalyst at room temperature. The method comprises the steps of mixing terminal alkyne compounds containing different substituent groups, N
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Paragraph 0052
(2021/05/12)
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- Decatungstate as Direct Hydrogen Atom Transfer Photocatalyst for SOMOphilic Alkynylation
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A versatile approach for the alkynylation of a variety of aliphatic hydrogen donors, including alkanes, is reported. We used tetrabutylammonium decatungstate as photocatalyst to generate organoradicals from C-H/Si-H bonds via hydrogen atom transfer. The l
- Capaldo, Luca,Ravelli, Davide
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supporting information
p. 2243 - 2247
(2021/04/05)
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- Predicting the catalytic activity of azolium-based halogen bond donors: an experimentally-verified theoretical study
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This report demonstrates the successful application of electrostatic surface potential distribution analysis for evaluating the relative catalytic activity of a series of azolium-based halogen bond donors. A strong correlation (R2> 0.97) was observed between the positive electrostatic potential of the σ-hole on the halogen atom and the Gibbs free energy of activation of the model reactions (i.e., halogen abstraction and carbonyl activation). The predictive ability of the applied approach was confirmed experimentally. It was also determined that the catalytic activity of azolium-based halogen bond donors was generally governed by the structure of the azolium cycle, whereas the substituents on the heterocycle had a limited impact on the activity. Ultimately, this study highlighted four of the most promising azolium halogen bond donors, which are expected to exhibit high catalytic activity.
- Bolotin, Dmitrii S.,Il'in, Mikhail V.,Novikov, Alexander S.,Suslonov, Vitalii V.,Sysoeva, Alexandra A.
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supporting information
p. 7611 - 7620
(2021/09/22)
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- Nickel-Catalyzed Difunctionalization of Alkynyl Bromides with Thiosulfonates and N -Arylthio Succinimides: A Convenient Synthesis of 1,2-Thiosulfonylethenes and 1,1-Dithioethenes
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An efficient nickel-catalyzed vicinal thiosulfonylation of 1-bromoalkynes with thiosulfonates in the presence of cesium carbonate is described. An operationally simple and highly regioselective atom transfer radical addition (ATRA) of alkynyl bromides provides a wide range of (E)-1,2-thiosulfonylethenes (α-aryl-β-thioarylvinyl sulfones) in moderate to high yields. The extensive substrate scope of both alkynyl bromides and thiosulfonates is explored with a broad range of functional groups. Indole-derived 1,1-bromoalkenes were also successfully explored in this 1,2-thiosulfonylation process. Moreover, the nickel-catalyzed geminal -dithiolation of alkynyl bromides with N -arylthio succinimides provides 1,1-dithioalkenes in high yields. The present protocol is reliable on gram scale, and a sequential one-pot bromination and thiosulfonylation of phenylacetylene is achieved in a scale-up synthesis. Following control experiments, a plausible mechanism is proposed to rationalize the experimental outcome and the vicinal thio-sulfonylation.
- Kumari, Arram Haritha,Kumar, Jangam Jagadesh,Krishna, Gamidi Rama,Reddy, Raju Jannapu
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supporting information
p. 2850 - 2864
(2021/05/18)
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- Copper-catalysed three-component carboiodination of arynes: Expeditious synthesis of: O -alkynyl aryl iodides
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A copper-catalysed three-component iodoalkynylation reaction of arynes for the expeditious and versatile synthesis of o-alkynyl aryl iodides has been developed. Mechanism research shows that the reaction goes through two steps enabled by copper catalysis: the formation of 1-iodo-2-arylacetylene and the insertion of the aryne into a C(sp)-I bond.
- Cao, Wenxuan,Niu, Sheng-Li,Shuai, Li,Xiao, Qing
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supporting information
p. 972 - 975
(2020/02/03)
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- Oxidant- and additive-free simple synthesis of 1,1,2-triiodostyrenes by one-pot decaroboxylative iodination of propiolic acids
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A metal- and oxidant-free facile synthesis of a range of 1,1,2-triiodostryrene derivatives has been developed which utilizes a simple decarboxylative triiodination of propiolic acids using molecular iodine and sodium acetate in a one-pot manner. Electron-
- Ghosh, Subhankar,Ghosh, Rajat,Chattopadhyay, Shital K.
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supporting information
(2020/09/15)
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- Preparation method of 1-iodoalkyne
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The invention discloses a preparation method of 1-iodoalkyne. The method comprises the following step: reacting a terminal alkyne compound with N-iodosuccinimide in a solvent in the presence of aluminum oxide and a molecular sieve to prepare a 1-iodoalkyn
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Paragraph 0009; 0016-0019
(2020/07/03)
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- Efficient synthesis of 1-iodoalkynes: Via Al2O3 mediated reaction of terminal alkynes and N -iodosuccinimide
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Iodination of terminal alkynes using N-iodosuccinimide (NIS) in the presence of γ-Al2O3 was developed to afford 1-iodoalkynes with good to excellent yields (up to 99%). This described approach featured excellent chemoselectivity, good functional group tolerance, and utilization of an inexpensive catalyst.
- Yao, Ming,Zhang, Jingjing,Yang, Sen,Xiong, Hangxing,Li, Li,Liu,Shi, Hong
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p. 3946 - 3950
(2020/02/04)
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- Synthesis method of 1-iodoalkyne compound
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The invention discloses a synthetic method of a 1-iodoalkyne compound. The method comprises the following steps: 1, preparing raw materials; the 1-iodoalkyne compound is prepared by reacting a terminal alkyne compound with N-iodosuccinimide in a solvent i
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Paragraph 0009; 0016-0017
(2020/06/20)
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- Acetic Acid Promoted Direct Iodination of Terminal Alkynes with N -Iodosuccinimide: Efficient Preparation of 1-Iodoalkynes
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An efficient and highly chemoselective approach for the direct iodination of terminal alkynes using acetic acid as N -iodosuccinimide activated reagent under metal-free conditions has been developed. This facile process tolerates a variety of terminal alkynes and provides the desired products in good to excellent yields (up to 99percent).
- Liu, Liu E.,Xiong, Hangxing,Yang, Sen,Yao, Ming,Zhang, Jingjing
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supporting information
p. 1102 - 1106
(2020/07/04)
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- Au(I)-Catalyzed Hydration of 1-Iodoalkynes Leading to α-Iodoketones
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A catalytic protocol for the Au(I)-catalyzed hydration of 1-iodoalkynes is disclosed. The use of Au(I)–NHC catalyst enabled the straightforward synthesis of a variety of α-iodomethyl ketones in good to excellent yields. The utility of this simple method is further highlighted by showcasing iodination/hydration and hydration/oxidation sequential protocols leading to the construction of molecular complexity.
- Cazin, Catherine S. J.,Gómez-Herrera, Alberto,Hashim, Ishfaq Ibni,Nahra, Fady,Porré, Marre
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supporting information
p. 6790 - 6794
(2020/11/23)
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- Copper(i) complexes bearing mesoionic carbene ligands: Influencing the activity in catalytic halo-click reactions
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Metal complexes of mesoionic carbene (MIC) ligands are known to catalyze a variety of chemical transformations. In this contribution, we report on the synthesis of a dicationic dicopper(i) complex containing a di-MIC ligand. Two routes are presented for the synthesis of the dicopper complex: Ag-mediated transmetalation and direct deprotonation. For the Ag-mediated transmetalation route, the detection and isolation of several Ag-containing intermediates that are relevant for the final formation of the aforementioned dicopper complex are reported. We then investigate a series of copper(i) complexes based on MIC ligands as precatalysts for the azide halo-alkyne (Click) cycloaddition reaction. In a comparative study, three different halide-containing (I, Br, Cl) substrates have been investigated with different catalysts to survey the behaviour for mono/di-copper-MIC complexes as well as neutral, mono- and di-cationic complexes. The cationic complexes proved to have superior activities compared to the neutral species. These are the first reports on the use of Cu-MIC complexes as precatalysts for the halo-Click reaction.
- Beerhues, Julia,Etzold, Oliver,Sarkar, Biprajit,Suntrup, Lisa
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supporting information
p. 15504 - 15510
(2020/11/18)
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- Borylative Heterocyclization without Air-Free Techniques
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In contrast to previously reported borylative heterocyclization methods, a reaction here proceeds without air-free techniques to access synthetically useful borylated thiophenes, benzothiophenes, and isocoumarins. A comparison of stability/decomposition rates in air of several catecholboronic ester (Bcat) compounds derived from different heterocycle cores showed a strong dependence on the heterocycle structure. Lessons learned from this comparison were then harnessed for the development of borylative heterocyclization reactions under ambient-atmosphere conditions and with wet solvent. In contrast to literature reports suggesting general moisture sensitivity, a subset of Bcat products resulting from this technique were chromatography-stable and directly isolable, obviating the requirement for an extra synthetic transformation into more stable boron species, such as pinacolboronic esters (Bpin), for isolation. The isolated Bcat products were amenable to various downstream functionalization reactions, including reactions that were not accessible with their better-known Bpin counterparts, showing the complementarity of Bcat reaction partners and expanding their known chemistry. These results suggest the value of conceptual revisitation of substitution and solvent influence on stability and isolability of organo-Bcat compound classes and lay the groundwork for development of additional practical borylative methods in air.
- Blum, Suzanne A.,Gao, Chao,Nakao, Shuichi
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p. 10350 - 10368
(2020/09/23)
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- Oxidative Addition of Alkenyl and Alkynyl Iodides to a AuI Complex
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The first isolated examples of intermolecular oxidative addition of alkenyl and alkynyl iodides to AuI are reported. Using a 5,5′-difluoro-2,2′-bipyridyl ligated complex, oxidative addition of geometrically defined alkenyl iodides occurs readily, reversibly and stereospecifically to give alkenyl-AuIII complexes. Conversely, reversible alkynyl iodide oxidative addition generates bimetallic complexes containing both AuIII and AuI centers. Stoichiometric studies show that both new initiation modes can form the basis for the development of C?C bond forming cross-couplings.
- Bower, John F.,Cadge, Jamie A.,Russell, Christopher A.,Sparkes, Hazel A.
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supporting information
p. 6617 - 6621
(2020/03/13)
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- Design, synthesis and comparative analysis of triphenyl-1,2,3-triazoles as anti-proliferative agents
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Herein, a series of triaryl-1,2,3-triazoles, in order to check cytotoxicity on breast cancer cell lines have been synthesized with pendent benzyl ring to mimic the phenolic A ring of Tamoxifene. The biological results indicated that most of the compounds
- Dheer, Divya,Behera, Chittaranjan,Singh, Davinder,Abdullaha, Mohd,Chashoo, Gousia,Bharate, Sandip B.,Gupta, Prem N.,Shankar, Ravi
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- Silver-Mediated Decarboxylative Fluorodiiodination of Alkynoic Acids: Synthesis of Regio- and Stereoselective Fluoroalkenes
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A variety of arylalkynoic acids reacted with 1,3-diiodo-5,5-dimethylhydantoin and HF·pyridine in the presence of AgOAc to provide the corresponding 1-fluoro-2,2-diiodovinylarenes in good yields and high regioselectivity. In addition, Pd-catalyzed cross-co
- Jayaraman, Aravindan,Lee, Sunwoo
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supporting information
p. 3485 - 3489
(2019/05/24)
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- Convenient Access to 2,3-Disubstituted-cyclobut-2-en-1-ones under Suzuki Conditions and Their Synthetic Utility
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A regioselective synthesis of general applicability has been designed for the one-pot preparation of 2,3-disubstituted-cyclobutenones from iodoalkynes through cyclobutenylation, Suzuki CC coupling, and ketone formation. This one-pot methodology has been a
- Alcaide, Benito,Almendros, Pedro,Lázaro-Milla, Carlos
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p. 7547 - 7552
(2019/04/30)
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- Iodination of terminal alkynes using KI/CuSO4 – A facile method with potential for radio-iodination
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Herein, we report an efficient new method for the iodination of terminal alkynes using stoichiometric KI and CuSO4 in a mix of acetonitrile and acetate buffer that holds promise for further development into a method for radio-iodination.
- Ferris, Trevor,Carroll, Laurence,Mease, Ronnie C.,Spivey, Alan C.,Aboagye, Eric O.
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supporting information
p. 936 - 939
(2019/03/04)
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- Concise and gram-scale total synthesis of lansiumamides A and B and alatamide
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The total synthesis of potent anti-obesity lansiumamide B was accomplished in four steps using commercially available materials. The synthetic strategy, featured with copper-catalyzed Buchwald coupling, is concise, convergent, practical and can be carried out on a one-gram scale. This approach could give either Z- or E-configured enamide moiety in natural products with absolute stereocontrol and was applied in the total synthesis of natural products.
- Lin, Ran,Lin, Xi,Su, Qian,Guo, Binbin,Huang, Yanqin,Ouyang, Ming-An,Song, Liyan,Xu, Huiyou
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- Synthesis of 5H-Selenopheno[3,2-c]isochromen-5-ones Promoted by Dialkyl Diselenides and Oxone
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We describe here for the first time the synthesis of isochromenones fused to selenophenes. 5H-Selenopheno[3,2-c]isochromen-5-ones were obtained through a double intramolecular cyclization of methyl 2-(organyl-1,3-diynyl)benzoate promoted by electrophilic species of selenium generated in situ by the reaction of dialkyl diselenides with Oxone, using ethanol as solvent. The reactions were conducted satisfactorily under mild conditions, using a range of 1,3-diynes and dialkyl diselenides as substrates. A total of sixteen unprecedent 5H-selenopheno[3,2-c]isochromen-5-ones were selectively obtained in moderate to good yields (40–86%) under reflux in an open flask and in short reaction times (1.0–2.5 h). (Figure presented.).
- Goulart, Helen A.,Neto, José S. S.,Barcellos, Angelita M.,Barcellos, Thiago,Silva, Márcio S.,Alves, Diego,Jacob, Raquel G.,Lenard?o, Eder J.,Perin, Gelson
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supporting information
p. 3403 - 3411
(2019/05/28)
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- Gold-Catalyzed C(sp2)?C(sp) Coupling by Alkynylation through Oxidative Addition of Bromoalkynes
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A gold(I)-catalyzed cascade cyclization–alkynylation of allenoates using alkynyl bromide to generate β-alkynyl-γ-butenolides was investigated. Whereas alkynyl iodides afforded significant amounts of the homo-coupling of two lactone units, alkynyl bromides led to a selective reaction, and a broad functional group tolerance was observed. Under the optimized reaction conditions, it was possible to directly synthesize a large range of β-alkynyl-γ-butenolides in moderate to good yields without the need for any external oxidant.
- Yang, Yangyang,Schie?l, Jasmin,Zallouz, Sirine,G?ker, Verena,Gross, Jürgen,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
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supporting information
p. 9624 - 9628
(2019/07/05)
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- An end [...] of 1, 3 - alkene alkyne class compound and its preparation and use
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The present invention provides a compound of formula (III) shown [...] of the end of the 1, 3 - alkene alkyne class compounds, the present invention through the aryl alkyne chlorine with the catalytic reaction for preparing aminoarylacetylenes, the tail e
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Paragraph 0030; 0043-0046
(2019/04/04)
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- Halogenated conjugated 1, 3 - alkene alkyne class compound and its preparation method and application
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The present invention provides a compound of formula (III) as shown by a halogenated conjugated 1, 3 - alkene alkyne class compounds, the present invention through the aryl alkyne chlorine with the catalytic reaction for preparing aminoarylacetylenes, one-step synthesis of halogenated conjugated 1, 3 - alkene alkyne class compounds, simple and convenient, such halogenated conjugated 1, 3 - enyne compound has anti-tumor activity, drug development system has broad application prospects in, with a view to the treatment of diseases related to providing a more effective way.
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Paragraph 0047-0051
(2019/03/23)
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- Regio- and Stereoselective Synthesis of Enynyl-Aryl Ethers Enabled by Copper/Iodide Tandem Catalysis
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An approach to preparing enynyl-aryl ethers from phenols and phenylacetylenes is described. This method without extra ligands, overcoming the favored Glaser-Hay dimerization of alkyne, features a wide substrate scope (38 examples including endofolliculina
- Wu, Yun-Bin,Xiao, Lin,Mao, Chun-Li,Zang, Zhong-Lin,Zhou, Cheng-He,Cai, Gui-Xin
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supporting information
p. 4461 - 4467
(2019/08/21)
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- Synthesis of fluoroalkylated alkynes: Via visible-light photocatalysis
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Fluoroalkylated alkynes, which are versatile building blocks for the synthesis of various biologically active organofluorine compounds, were synthesized from easily available alkynyl halides and fluoroalkyl halides by visible-light photocatalysis. Addition of fluoroalkyl radicals to alkynes and subsequent dehalogenation selectively yielded fluoroalkylated alkynes.
- Iqbal, Naila,Iqbal, Naeem,Han, Sung Su,Cho, Eun Jin
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supporting information
p. 1758 - 1762
(2019/02/20)
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- Iodine-DMSO-promoted divergent reactivities of arylacetylenes
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An unprecedented set of efficient, economical, atom-economic and exceedingly selective I2-DMSO-promoted methods is described for the generation of different structures. The reaction represents the first of its kind, involving the use of different iodine concentrations, temperatures, acids and salt to adjust the selectivity for the synthesis of different alkenes, α-functionalized ketones and α-ketomethylthioesters.
- Rather, Suhail A.,Kumar, Atul,Ahmed, Qazi Naveed
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supporting information
p. 4511 - 4514
(2019/04/26)
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- Gold Catalyzed Photoredox C1-Alkynylation of N-Alkyl-1,2,3,4- tetrahydroisoquinolines by 1-Bromoalkynes with UVA LED Light
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A synthetic method that combines [Au2(m-dppm)2]Cl2 (dppm=bis(diphenylphosphanyl)methane) and UVA LED (LED=light emitting diode) light (365 nm) to catalyze the regioselective C1-alkynylation of N-alkyl-1,2,3,4-tetrahydroisoquinolines (THIQs) with alkynyl bromides is described. The reaction mechanism was delineated to involve a reductive quench pathway to generate the two posited radical species of the nitrogen-containing heterocycle and organic halide. In contrast, radical formation via an oxidative quench pathway was suggested to be operative in analogous control experiments with a 1-iodoalkyne. The usefulness of this carbon-carbon bond forming strategy was also exemplified by its application to the formal synthesis of the opioid analgesic drug methopholine and synthesis of a protoberberine alkaloid derivative.
- Zhao, Yichao,Jin, Jianwen,Chan, Philip Wai Hong
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supporting information
p. 1313 - 1321
(2019/06/03)
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- Chemoselective and stereospecific iodination of alkynes using sulfonium iodate(i) salt
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An efficient and highly chemoselective iodination of alkynes using a sulfonium iodate(i) electrophilc reagent under metal-free conditions has been realized. The reactivity of sulfonium iodate(i) salt could be significantly diverse in the presence of water
- Rao, Dodla S.,Reddy, Thurpu R.,Kashyap, Sudhir
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supporting information
p. 1508 - 1518
(2018/03/08)
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- Chloramine Salt Mediated Oxidative Halogenation of Terminal Alkynes with KI or NaBr: Practical Synthesis of 1-Bromoalkynes and 1-Iodoalkynes
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A direct oxidative halogenation of terminal alkynes has been realized using chloramine-B as the oxidant and KI or NaBr as the halogen source. This reaction enables a general and practical access to synthetically valuable 1-bromoalkynes and 1-iodoalkynes i
- Liu, Xiaozu,Chen, Guojun,Li, Chenglong,Liu, Peijun
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p. 2051 - 2055
(2018/09/18)
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- Novel synthesis of 5-iodo-1,2,3-triazoles using an aqueous iodination system under air
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A novel aqueous iodination system was developed for the synthesis of 5-iodo-1,2,3-triazoles under air. This reaction system has high efficiency and excellent chemo-selectivity with wide functional group tolerance. In addition, this method can be utilized
- Li, Lingjun,Xing, Xiaofang,Zhang, Chi,Zhu, Anlian,Fan, Xincui,Chen, Changpo,Zhang, Guisheng
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p. 3563 - 3566
(2018/08/31)
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- Efficient synthesis of alkynyl amides via aminocarbonylation of iodoalkynes
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Iodoethynylbenzene as iodoalkyne model compound was aminocarbonylated with tert-butylamine under carbon monoxide atmosphere in the presence of in situ palladium(0) catalysts. The formation of the unsaturated carboxamide (alkynyl amide) is always accompanied by that of the Glaser coupling product, diphenylbutadiyne. The yield of the amide-forming reaction was optimised by the systematic variation of the phosphine ligand, carbon monoxide pressure and temperature. The scope of the reaction was investigated by using various primary and secondary amines including amino acid methyl esters as N-nucleophiles. 17α-(Iodoethynyl)-testosterone was also functionalised by using this methodology providing the corresponding 17α-(carboxamidoethynyl)-testosterone derivatives in up to 96% yields. The reaction was extended to 1-(iodoethynyl)cyclohex-1-ene and 1-iodohex-1-yne. Ethyl iodopropiolate gave the enamine type product by the addition of amine to the alkyne functionality which was formed from the iodoalkyne via deiodination under standard aminocarbonylation conditions. The bromo analogue, bromoethynylbenzene has shown lower reactivity than the corresponding iodo derivative.
- Szuroczki, Péter,Boros, Borbála,Kollár, László
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p. 6129 - 6136
(2018/09/14)
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- Light-Driven Intermolecular Charge Transfer Induced Reactivity of Ethynylbenziodoxol(on)e and Phenols
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Ethynylbenziodoxol(on)es (EBXs) have been widely used in organic synthesis as electrophilic alkyne-transfer reagents involving carbon- and heteroatom-based nucleophiles. However, potential reactions of EBXs with phenols remain uninvestigated. Here, we present the formation of (Z)-2-iodovinyl phenyl ethers with excellent regio- and stereoselectivity through the reactivity between EBXs and phenols driven by visible light. We propose that this light-activated transformation proceeds through electron donor-acceptor complexes to enable new reactivity beyond existing mechanisms for alkynylation of carbon- and heteroatom-based nucleophiles. This operationally robust process was employed for the synthesis of diverse (Z)-2-iodovinyl phenyl ethers through irradiating a solution containing a phenyl-EBX, a phenol, and the base Cs2CO3 with a commercially available blue LED at room temperature. The (Z)-2-iodovinyl phenyl ether products can be further stereospecifically functionalized to form trisubstituted alkenes, demonstrating the potential of these products en route to chemical complexity.
- Liu, Bin,Lim, Chern-Hooi,Miyake, Garret M.
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supporting information
p. 12829 - 12835
(2018/10/15)
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- Systematic Experimental and Computational Studies of Substitution and Hybridization Effects in Solid-State Halogen Bonded Assemblies
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A quantitative assessment of the substituent, hybridization, and crystal-packing effects on the electronic, structural, and vibrational properties of halogen bonded systems is presented. Through a combined experimental and theoretical approach employing R
- Nguyen, Suong T.,Ellington, Thomas L.,Allen, Katelyn E.,Gorden, John D.,Rheingold, Arnold L.,Tschumper, Gregory S.,Hammer, Nathan I.,Watkins, Davita L.
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p. 3244 - 3254
(2018/05/09)
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- General Method for the Synthesis of 1,4-Disubstituted 5-Halo-1,2,3-triazoles
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A general method for the synthesis of 1,4-disubstituted 5-halo-1,2,3-triazoles has been developed. The one-pot two-step process consists of a CuAAC reaction of a copper(I) acetylide with an organic azide catalyzed by (aNHC)CuCl, followed by halogenation with N-chlorosuccinimide, N-bromosuccinimide, or I2.
- Gribanov, Pavel S.,Topchiy, Maxim A.,Karsakova, Iuliia V.,Chesnokov, Gleb A.,Smirnov, Alexander Yu.,Minaeva, Lidiya I.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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p. 5225 - 5230
(2017/09/29)
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- Hypervalent Iodine Mediated Chemoselective Iodination of Alkynes
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Reported herein are practical approaches for the chemoselective mono-, di-, and tri-iodination of alkynes based on efficient oxidative iodinations catalyzed by hypervalent iodine reagents. The reaction conditions were systematically optimized by altering
- Liu, Yan,Huang, Daya,Huang, Ju,Maruoka, Keiji
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p. 11865 - 11871
(2017/11/24)
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- Synthesis method of phenylethynyl iodine compound
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The invention discloses a synthesis method of a phenylethynyl iodine compound. According to the synthesis method, a phenylacetylene reaction substrate is used as a raw material and reacts with zinc diiodide and tert-butyl nitrite in the presence of an org
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Paragraph 0035; 0036; 0037
(2018/01/17)
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- Method for synthesizing 1-iodo-alkyne in high-selectivity manner
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The invention belongs to the technical field of synthetic chemistry and particularly relates to a method for synthesizing 1-iodo-alkyne in a high-selectivity manner. The method is mild in reaction condition, controllable in reaction product, single in pro
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Paragraph 0036-0038
(2017/08/30)
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- Highly efficient and recyclable catalyst for the direct chlorination, bromination and iodination of terminal alkynes
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Direct halogenation, including chlorination, bromination and iodination of terminal alkynes, are of great importance in organic synthesis. Here an efficient and recyclable nano-Ag/g-C3N4 catalyst system was developed and proved to be remarkably active with 39 examples varied from chlorination, bromination to iodination, of which 14 runs have yielded more than 95% of the product. Recycling of the catalyst was also achieved without obvious activity loss after several runs: 99% yield was observed even after 5 runs in the bromination of phenylacetylene. The catalysts system is of low cost and easy to be prepared, making this procedure versatile, convenient and economic.
- Shi, Wei,Guan, Zhipeng,Cai, Peng,Chen, Hao
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p. 199 - 204
(2017/08/10)
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- Switching of Regioselectivity in a Perfluorohexyl Iodide Mediated Synthesis of Phenylimidazo[1,2-a]pyridines
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3-Phenylimidazo[1,2-a]pyridines were synthesized through the perfluorohexyl iodide mediated coupling of 2-aminopyridines and phenylacetylenes. In situ iodination of the terminal alkyne by perfluorohexyl iodide reverses the polarity by generating a transient electrophilic iodoalkyne, and this alters the regioselectivity of the phenyl group. The reaction then proceeds by tandem electrophilic alkynylation and cyclization to form the fused-ring product. The protocol affords the 3-phenyl isomer with full regioselectivity and is complementary to reported methodologies for the synthesis of the 2-phenyl isomer starting from the same substrates.
- Roslan, Irwan Iskandar,Chuah, Gaik-Khuan,Jaenicke, Stephan
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supporting information
p. 671 - 675
(2017/02/05)
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- β-CD/CuI catalyzed regioselective synthesis of iodo substituted 1,2,3-triazoles, imidazo[1,2-a]-pyridines and benzoimidazo[2,1-b]thiazoles in water and their functionalization
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An environment benign process has been developed for the regioselective synthesis of 5-iodo-1,4-disubstituted-1,2,3-triazoles catalyzed by CuI/β-CD in water. Moreover, the process was manifested for the efficient synthesis of 2-iodo-imidazo[1,2-a]pyridine
- Dheer, Divya,Rawal, Ravindra K.,Singh, Virender,Sangwan,Das, Parthasarathi,Shankar, Ravi
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p. 4295 - 4306
(2017/06/30)
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- Copper-Catalyzed Hydrogen/Iodine Exchange in Terminal and 1-Iodoalkynes
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Detailed kinetic profiles of the copper-catalyzed exchange between the acetylenic proton and iodide of terminal and 1-iodophenylacetylenes are reported. The electronic nature of the alkynes does not influence the equilibrium of the exchange (Keq/sub
- Chung, Ryan,Vo, Anh,Hein, Jason E.
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p. 2505 - 2510
(2017/06/01)
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- A Base-Free Multicomponent Domino Approach: One-Pot Synthesis of 2-Iminothiazolines via Oxy-Iodination of Arylacetylenes
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A simple and an efficient multicomponent domino protocol is developed for the synthesis of 2-iminothiazolines starting from simple and readily available arylacetylenes, amines, and phenyl isothiocyanates under base-free conditions. The present method invo
- Kumar, G. Santosh,Kumar, A. Sanjeeva,Meshram
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supporting information
p. 399 - 403
(2016/02/09)
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- The Propargyl Rearrangement to Functionalised Allyl-Boron and Borocation Compounds
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A diverse range of Lewis acidic alkyl, vinyl and aryl boranes and borenium compounds that are capable of new carbon–carbon bond formation through selective migratory group transfer have been synthesised. Utilising a series of heteroleptic boranes [PhB(Cs
- Wilkins, Lewis C.,Lawson, James R.,Wieneke, Philipp,Rominger, Frank,Hashmi, A. Stephen K.,Hansmann, Max M.,Melen, Rebecca L.
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supporting information
p. 14618 - 14624
(2016/10/03)
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- Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes
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The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.
- Gómez-Herrera, Alberto,Nahra, Fady,Brill, Marcel,Nolan, Steven P.,Cazin, Catherine S. J.
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p. 3381 - 3388
(2016/11/16)
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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 00255-00256
(2015/05/26)
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- Scope and limitations of the intermolecular furan-yne cyclization
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Different types of alkynes were reacted with 2,5-disubstituted furans in order to evaluate the scope of the intermolecular furan-yne reaction. With ethynyl aryl ethers as starting materials, 2-phenoxy phenols were accessible in moderate to good yields. A different reaction mode was observed for alkynes bearing electron-withdrawing substituents. For these starting materials a cis-selective hydroarylation took place in an anti-Markovnikov fashion in excellent yields. 1,2-Diynes turned out to be suitable starting materials as well. Due to the second alkynyl moiety, after an initial phenol synthesis, a subsequent hydro-alkoxylation by the newly formed phenolic oxygen gives access to benzofurans in a tandem process.
- Zeiler, Anna,Ziegler, Michael J.,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
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supporting information
p. 1507 - 1514
(2015/08/04)
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- Regioselective Synthesis of Polyheterohalogenated Naphthalenes via the Benzannulation of Haloalkynes
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Independent control of halide substitution at six of the seven naphthalene positions of 2-arylnaphthalenes is achieved through the regioselective benzannulation of chloro-, bromo-, and iodoalkynes. The modularity of this approach is demonstrated through the preparation of 44 polyheterohalogenated naphthalene products, most of which are difficult to access through known naphthalene syntheses. The outstanding regioselectivity of the reaction is both predictable and proven unambiguously by single-crystal X-ray diffraction for many examples. This synthetic method enables the rapid preparation of complex aromatic systems poised for further derivatization using established cross-coupling methods. The power and versatility of this approach makes substituted naphthalenes highly attractive building blocks for new organic materials and diversity-oriented synthesis.
- Lehnherr, Dan,Alzola, Joaquin M.,Lobkovsky, Emil B.,Dichtel, William R.
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supporting information
p. 18122 - 18127
(2015/12/24)
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- Identification of a new p53/MDM2 inhibitor motif inspired by studies of chlorofusin
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Previous studies on the natural product chlorofusin have shown that the full peptide and azaphilone structure are required for inhibition of the interaction between MDM2 and p53. In the current work, we utilized the cyclic peptide as a template and introd
- Cominetti, Marco M.D.,Goffin, Sarah A.,Raffel, Ewan,Turner, Kerrie D.,Ramoutar, Jordann C.,O'Connell, Maria A.,Howell, Lesley A.,Searcey, Mark
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supporting information
p. 4878 - 4880
(2015/10/28)
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