10498-35-8Relevant academic research and scientific papers
THE CIS CHLORINATION OF ALKENES USING SELENIUM REAGENTS
Morella, Angelo M.,Ward, A. David
, p. 1197 - 1200 (1984)
The phenylselenenyl chloride adduct from alkenes can be oxidised and the seleno moiety can be displaced by chloride to give high yields of dichlorides with cis geometry.
A NOVEL ONE-STEP OXIDATION OF TERMINAL EPOXIDES TO ALLYLIC ALDEHYDES
Willis, Christine L.
, p. 2175 - 2178 (1987)
Various gibberellin epoxides have been oxidized with sulphuryl chloride to α,β-unsaturated aldehydes in >70percent isolated yield.This novel one-step oxidation occurs in the presence of hydroxy (except at C-13) ester, lactone and olefinic functions.
Organoselenium-catalyzed vicinal dichlorination of unsaturated phosphonates
Zeng, Xianghua,Gong, Chunhua,Zhang, Junyong,Xie, Jingli
, p. 7866 - 7871 (2016)
Diphenyl diselenide (PhSeSePh) was effective as a pre-catalyst for the vicinal dichlorination of α,β-unsaturated phosphonates with sulfuryl chloride. The reaction conditions were mild and the desired products were formed in up to 93% yield and moderate diastereoselectivity (10:1). The important diphenylselenium dichloride intermediate was obtained and characterized by X-ray crystallography.
Chlorination of Cyclohexene by Copper(II) Chloride
Gamlen, Philip H.,Henty, Michael S.,Roberts, Hugh L.
, p. 1373 - 1376 (1983)
Evidence is presented which indicates that CuCl+ is the reactive species in the chlorination of cyclohexene by copper(II) chloride in acetonitrile.The reaction is retarded by an excess of chloride ion and by copper(I) salts, and accelerated by aluminium trichloride.A kinetic scheme which accounts for these observations is suggested.
Catalytic, stereospecific syn-dichlorination of alkenes
Cresswell, Alexander J.,Eey, Stanley T.-C.,Denmark, Scott E.
, p. 146 - 152 (2015)
As some of the oldest organic chemical reactions known, the ionic additions of elemental halogens such as bromine and chlorine to alkenes are prototypical examples of stereospecific reactions, typically delivering vicinal dihalides resulting from anti-addition. Although the invention of enantioselective variants is an ongoing challenge, the ability to overturn the intrinsic anti-diastereospecificity of these transformations is also a largely unsolved problem. Here, we describe the first catalytic, syn-stereospecific dichlorination of alkenes, employing a group transfer catalyst based on a redox-active main group element (selenium). With diphenyl diselenide (PhSeSePh) (5amol%) as the pre-catalyst, benzyltriethylammonium chloride (BnEt 3 NCl) as the chloride source and an N-fluoropyridinium salt as the oxidant, a wide variety of functionalized cyclic and acyclic 1,2-disubstituted alkenes, including simple allylic alcohols, deliver syn-dichlorides with exquisite stereocontrol. This methodology is expected to find applications in streamlining the synthesis of polychlorinated natural products such as the chlorosulfolipids.
The Electrochemical cis-Chlorination of Alkenes
Strehl, Julia,Fastie, Cornelius,Hilt, Gerhard
supporting information, p. 17341 - 17345 (2021/10/23)
The first example for the electrochemical cis-dichlorination of alkenes is presented. The reaction can be performed with little experimental effort by using phenylselenyl chloride as catalyst and tetrabutylammoniumchloride as supporting electrolyte, which also acts as nucleophilic reagent for the SN2-type replacement of selenium versus chloride. Cyclic voltammetric measurements and control experiments revealed a dual role of phenylselenyl chloride in the reaction. Based on these results a reaction mechanism was postulated, where the key step of the process is the activation of a phenylselenyl chloride-alkene adduct by electrochemically generated phenylselenyl trichloride. Like this, different aliphatic and aromatic cyclic and acyclic alkenes were converted to the dichlorinated products. Thereby, throughout high diastereoselectivities were achieved for the cis-chlorinated compounds of >95 : 5 or higher.
IONIC METHYLATION OF DICHLORO- AND DIBROMOALKANES
Parnes, Z. N.,Romanova, V. S.,Vol'pin, M. E.
, p. 258 - 260 (2007/10/02)
The dichloro and dibromo derivatives of hydrocarbons are methylated by the action of tetramethylsilane in the presence of aluminum bromide with the formation of hydrocarbons containing a quaternary carbon atom irrespective of whether the halogen atoms are at one or at different carbon atoms.
Peroxide-induced α-Elimination of Organic Halides from Organotellurium(IV) Halides
Uemura, Sakae,Fukuzawa, Shin-ichi
, p. 1033 - 1034 (2007/10/02)
Treatment of organotellurium(IV) halides with t-butyl hydroperoxide in 1,4-dioxan, acetic acid, or acetonitrile affords the corresponding organic halides in good to moderate yields presumably as the result of a 1,2-halogen shift.
Three-Component Reactions. VIII. Chlorination of Olefines in N-Methylpyrrolidone
Beger, J.,Jacobi, R.,Storch, A.,Ullmann, M.
, p. 394 - 400 (2007/10/02)
The chlorination of cyclohexene, styrene and 1-dodecene in NMP gives immonium-chlorides 5 reacting with water to β-chloralkyl-γ-N-methylaminobutyrat-hydrochlorides.With cyclohexene the reaction proceeds stereospecifically as trans-addition.From styrene there is only formed the Markovnikov product, and from dodecene a mixture of isomeres is obtained containing about 30percent of the anti-Markovnikov product.
