13294-30-9Relevant academic research and scientific papers
Ruthenium-catalyzed transformation of alkenyl triflates to alkenyl halides
Shirakawa, Eiji,Imazaki, Yusuke,Hayashi, Tamio
supporting information; experimental part, p. 5088 - 5090 (2009/12/08)
In the presence of a ruthenium catalyst, alkenyl triflates were found to be transformed to the corresponding bromides, chlorides and iodides simply by treatment with a lithium halide (1.2 equiv.). The Royal Society of Chemistry 2009.
Ring-fused and spiro cyclopentenones by Ni(CO)4-promoted intermolecular carbonylative cycloaddition of acetylenes with 3-halo- and 1-(halomethyl)cycloalkenes
Pagès, Lluís,Llebaria, Amadeu,Camps, Francisco,Molins, Elies,Miravitlles, Caries,Moretó, Josep M.
, p. 10449 - 10461 (2007/10/02)
The title carbonylative cycloaddition of five- to eight-member ring 3-halo- and 1-(halomethyl)cycloalkenes with different acetylenes was studied. From moderate to good yields of ring-fused and spiro cyclopentenone derivatives were obtained, especially in the reaction with acetylenes bearing electron-withdrawing substituents by proper selection of the reaction conditions to avoid the acetylene polyinsertion and/or other side reactions from the organonickel intermediates. In this context, the beneficial role of acetate ion on the outcome of the reaction is rationalized. This process leading to the formation of bicycloadducts with the concomitant formation of up to six C-C bonds, with high regio- and stereoselectivity, can be useful in the synthesis of natural products as exemplified by the easy preparation of [5-5-5] tricyclic compound 14 from a 1:1 cis and trans isomeric mixture of 6-acetoxy-3-bromocyclooctene (11). A plausible general reaction mechanism is proposed that is consistent with all the products obtained.
Phenylselenium Trichloride in Organic Synthesis. Reaction with Unsaturated Compounds. Preparation of Vinylic Chlorides via Selenoxide Elimination
Engman, Lars
, p. 4086 - 4094 (2007/10/02)
Phenylselenium trichloride, PhSeCl3, was reacted with a number olefinic compounds to produce (β-chloroalkyl)phenylselenium dichlorides.The addition was anti stereospecific and irreversible.The presence of an oxygen substituent (acyloxy or aryloxy group) in the allylic position of the olefin directed the attack of PhSeCl3 to occur regiospecifically anti-Markovnikov to give a (β-acyloxy/aryloxy-β'-chloroalkyl)phenylselenium dichloride.When the (β-chloroalkyl)phenylselenium dichlorides were treated in methylene chloride with aqueous sodium hydrogen carbonate, the selenium dichloride moiety was readily hydrolyzed to a selenoxide, which underwent the usual selenoxide elimination reaction to produce an allylic or a vinylic chloride.Symmetrical olefins containing no allylic hydrogens were converted to vinylic chlorides with retention of olefin geometry.Olefins containing a directing oxygen substituent in the allylic position afforded vinylic chlorides where the vinylic halogen atom was oriented 1,3 to the oxygen substituent (E/Z mixture).Other olefins afforded mixtures of allylic and vinylic halides in varying proportions.The reaction of phenyselenium tribromide, PhSeBr3, with some olefinic compounds was also investigated.This material showed the same stereo- and regiochemical behavior as PhSeCl3 in its addition reactions.However, the adducts were not useful for the preparation of vinylic or allylic bromides by using the hydrolytic selenoxide elimination reaction.
PREPARATION OF POLYHALOGENOCYCLOPROPANES BY ADDITION OF HALOGENOCARBENES TO HALOGENO-ALKENES UNDER PHASE TRANSFER CONDITIONS
Baird, Mark. S.,Nethercott, William,Slowey, Paul D.
, p. 3815 - 3829 (2007/10/02)
A range of 1-halogenocycloalkenes, 2-halogeno-alkenes, and 1-halogeno- and 1,1-dihalogeno-2-methylprop-1-enes are converted to polyhalogenocyclopropanes by reaction with dichloro- or dibromocarbenes, generated from the haloform and aqueous base in the pre
COMPARISON OF SYN DEHYDROHALOGENATIONS FROM TANS-1-BROMO-2-CHLOROCYCLOALKENES PROMOTED BY COMPLEX BASE AND BY POTASSIUM TERT-BUTOXIDE
Croft, Alan P.,Bartsch, Richard A.
, p. 2737 - 2740 (2007/10/02)
Compared with t-BuOK-t-BuOH, syn eliminations from trans-1-bromo-2-chlorocycloalkanes (C4-C8) induced by NaNH2-NaO-t-Bu in THF are rapid, exhibit greater propensity for dehydrochlorination and show little sensitivity to ring size of the dihalocycloalkane.
Photochemistry of Alkyl Halides. 10. Vinyl Halides and Vinylidene Dihalides
Kropp, Paul J.,McNeely, Steven A.,Davis, Robert Drummond
, p. 6907 - 6915 (2007/10/02)
The photobehavior of the acyclic vinyl iodide 2, the 1-iodocycloalkenes 11-14 and 39, the (halomethylene)cycloalkanes 45-48, and the (dihalomethylene)cyclohexanes 62-64 has been studied.Except for the dichloride 64, which exhibited only radical behavior, each of the halides afforded a mixture of ionic and radical products.The two bromides studied, 48 and 63, afforded lower ratios of ionic to radical products than the corresponding iodides 45 and 62.Irradiation of vinyl iodides was found to be a convenient and powerful method for the generation of vinyl cations, including the highly strained 1-cyclohexenyl and 1-cyclopentenyl cations and the unstabilized α-unsubstituted cations 51 and 54.The latter cations underwent rearrangement to the ring-expanded 1-cycloalkenyl cations 28 and 36, respectively.Lowering the temperature of the irradiation of iodides 13, 14, and 45 resulted in an increased ratio of ionic to radical products.However, iodide 47, which underwent principally fragmentation to enyne 61, showed little temperature effect.
A DIRECT SYNTHESIS OF 1-CYCLOALKENYLPHOSPHONATES
Banerjee, Shyamal,Engel, Robert,Axelrad, George
, p. 15 - 18 (2007/10/02)
A series of 1-cycloalkenylphosphonoate diesters has been synthesized starting with the corresponding vinylic chlorides.This has been accomplished using the Cu(I) complexes of triethyl phosphite in a direct reaction with the vinylic chlorides.This represen
