142572-49-4Relevant academic research and scientific papers
Copper-mediated nucleophilic displacement reactions of 1-haloalkynes. Halogen-halogen exchange and sulfonylation
Abe, Hajime,Suzuki, Hitomi
, p. 787 - 798 (1999)
Some copper(I) and (II) compounds have been found to act as efficient reagents for the nucleophilic displacement of 1-haloalkynes. Copper(I) iodide smoothly transforms 1-bromoalkynes (2) into 1-iodoalkynes (1) which, on further treatment with copper(II) bis(arenesulfinate), are readily converted to the corresponding alkynyl aryl sulfones (4). The kinetic data of the halogen exchange between (4-chlorophenyl)ethynyl bromide (2d) and CuI have shown that the reaction is linearly dependent on the concentrations of both compounds. A mechanistic pathway involving the single electron transfer between 1-haloalkynes and copper(I) salt has been proposed for the present copper-assisted halogen exchange reaction at acetylenic carbon atom.
A new straightforward synthesis of alkynyl sulfones via the sonochemical coupling between alkynyl halides and copper sulfinates
Suzuki, Hitomi,Abe, Hajime
, p. 3717 - 3720 (1996)
Alkynyl aryl sulfones 2 were easily obtained in moderate to good yields by treating alkynyl iodides 1 with copper arenesulfinates in a tetrahydrofuran suspension under ultrasonic irradiation.
Trifluoromethyl Nonaflate: A Practical Trifluoromethoxylating Reagent and its Application to the Regio- and Stereoselective Synthesis of Trifluoromethoxylated Alkenes
Hammond, Gerald B.,Kumon, Tatsuya,Lu, Zhichao,Umemoto, Teruo
, p. 16171 - 16177 (2021/06/27)
The trifluoromethoxy group has elicited much interest among drug and agrochemical discovery teams because of its unique properties. We developed trifluoromethyl nonafluorobutanesulfonate (nonaflate), TFNf, an easy-to-handle, bench-stable, reactive, and scalable trifluoromethoxylating reagent. TFNf is easily and safely prepared in a simple process in large scale and the nonaflyl part of TFNf can easily be recovered as nonaflyl fluoride after usage and recycled. The synthetic potency of TFNf was showcased with the underexplored synthesis of various trifluoromethoxylated alkenes, through a high regio- and stereoselective hydro(halo)trifluoromethoxylation of alkyne derivatives such as haloalkynes, alkynyl esters, and alkynyl sulfones. The synthetic merits of TFNf were further underscored with a high-yielding and smooth nucleophilic trifluoromethoxylation of alkyl triflates/bromides and primary/secondary alcohols.
Stereoselective silylcupration of conjugated alkynes in water at room temperature
Linstadt, Roscoe T. H.,Peterson, Carl A.,Lippincott, Daniel J.,Jette, Carina I.,Lipshutz, Bruce H.
supporting information, p. 4159 - 4163 (2014/05/06)
Micellar catalysis enables copper-catalyzed silylcupration of a variety of electron-deficient alkynes, thereby providing access to isomerically pure E- or Z-β-silyl-substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially tolerant of functional groups present in the substrates. The aqueous reaction medium has been successfully recycled several times, and a substrate/catalyst ratio of 10,000:1 has been documented for this methodology. Fast, cheap, and green: Micellar catalysis enables the selective construction of a variety β-silyl-substituted carbonyl derivatives under mild aqueous conditions. The reaction is catalyzed by low levels of CuI, is compatible with numerous electron-withdrawing groups, affords high yields, and provides opportunities for scale-up and recycling of the reaction medium. The environmental impact, as measured by E Factors, is very low.
CAN mediated reaction of aryl sulfinates with alkenes and alkynes: Synthesis of vinyl sulfones, β-iodovinyl sulfones and acetylenic sulfones
Nair, Vijay,Augustine, Anu,Suja
, p. 2259 - 2265 (2007/10/03)
Cerium(IV) ammonium nitrate (CAN) mediated reaction of aryl sulfinates and sodium iodide with alkenes afforded vinyl sulfones in very good yields. Alkynes underwent similar reaction to give β-iodovinyl sulfones, which on treatment with potassium carbonate
A convenient new route to piperidines, pyrrolizidines, indolizidines, and quinolizidines by cyclization of acetylenic sulfones with β- and γ-chloroamines. Enantioselective total synthesis of indolizidines (-)-167B, (-)-209D, (-)-209B, and (-)-207A
Back, Thomas G.,Nakajima, Katsumasa
, p. 4543 - 4552 (2007/10/03)
The methyl esters of (L)-phenylalanine and (L)-methionine underwent conjugate additions via their free amino groups to 1-(p-toluenesulfonyl)hexyne, followed by intramolecular acylation of the corresponding enamide anions and tautomerization to afford 2-benzyl-5-n-butyl-3-hydroxy-4-(p-toluenesulfonyl)pyrrole and 5-n-butyl-3-hydroxy-2-(2-methylthioethyl)-4-(p-toluenesulfonyl)pyrrole, respectively. The conjugate additions of a series of acyclic and cyclic secondary β- and γ-chloroamines to acetylenic sulfones proceeded similarly under mild conditions. The resulting adducts were deprotonated with LDA in THF at -78 °C, and the resulting sulfone-stabilized carbanions underwent intramolecular alkylation to afford cyclic enamine sulfones. Thus, acyclic γ-chloroalkylbenzylamines afforded the corresponding 2- or 2,6-disubstituted piperidines, while 2-(chloromethyl)-pyrrolidines, 2-(2-chloroethyl)pyrrolidines, 2-(chloromethyl)piperidines, and 2-(2-chloroethyl)-piperidines produced the corresponding 3-substituted pyrrolizidines, 5- or 3-substituted indolizidines, and 4-substituted quinolizidines, respectively. 8-Methyl-5-substituted indolizidines were also prepared from the appropriate methyl-substituted chloroamine precursor. Enantioselective syntheses were achieved by employing chiral chloroamines derived from amino acids or other enantiopure precursors. Further transformations of several of the products provided concise syntheses of four dendrobatid alkaloids. Thus, reduction of (8aS)-5-n-propyl-6-(p-toluenesulfonyl)-Δ-indolizidine with sodium cyanoborohydride in trifluoroacetic acid, followed by reductive desulfonylation, afforded (-)-indolizidine 167B. The corresponding 5-n-hexyl derivative similarly produced (-)-indolizidine 209D, while (-)-(8R,8aS)-8-methyl-5-n-pentyl-6-(p-toluenesulfonyl)-Δ5,6-indolizidine furnished (-)-indolizidine 209B. Finally, the similar reduction and debenzylation of (-)-(8R,8aS)-5-(2-benzyloxyethyl)-8-methyl-6-(p-toluenesulfonyl)-Δ-indolizid ine produced the corresponding 5-hydroxyethyl indolizidine. This was subjected to chlorination of the alcohol group with thionyl chloride and substitution with a higher order allyl cuprate reagent to afford (-)-indolizidine 207A.
Reactions of (E)-2-Iodo-1-tosyl-1-alkenes as Useful Synthetic Intermediates
Iwata, Noriyoshi,Morioka, Tetsuro,Kobayashi, Toshifumi,Asada, Takahiro,Kinoshita, Hideki,Inomata, Katsuhiko
, p. 1379 - 1388 (2007/10/02)
(E)-2-Iodo-1-tosyl-1-alkenes readily available by iodosulfonization of 1-alkynes were found to be useful synthons for the regio- and/or stereoselective preparation of 1-tosyl-1-alkynes, 1-tosyl-2-alkynes, (Z)-vinyl and (Z)-allyl sulfones, β-tosyl enamines
