56745-19-8Relevant articles and documents
Zn(II)- or Rh(I)-catalyzed rearrangement of silylated [1,1'-Bi(cyclopropan) ]-2'-en-1-ols
Zhang, Hang,Li, Changkun,Xie, Guojun,Wang, Bo,Zhang, Yan,Wang, Jianbo
, p. 6286 - 6293 (2014/07/21)
The rearrangement reactions of silylated alcohols bearing the highly strained structures of cyclopropene and cyclopropanol connected in adjacent positions have been studied under ZnI2- and Rh(I)-catalyzed conditions. The results show intriguing
Selective iron-catalyzed cross-coupling reactions of Grignard reagents with enol triflates, acid chlorides, and dichloroarenes
Scheiper, Bodo,Bonnekessel, Melanie,Krause, Helga,Fuerstner, Alois
, p. 3943 - 3949 (2007/10/03)
Cheap, readily available, air stable, nontoxic, and environmentally benign iron salts such as Fe(acac)3 are excellent precatalysts for the cross-coupling of Grignard reagents with alkenyl triflates and acid chlorides. Moreover, it is shown that dichloroarene and -heteroarene derivatives as the substrates can be selectively monoalkylated by this method. All cross-coupling reactions proceed very rapidly under notably mild conditions and turned out to be compatible with a variety of functional groups in both reaction partners. A detailed analysis of the preparative results suggests that iron-catalyzed C-C bond formations can occur via different pathways. Thus, it is likely that reactions of methylmagnesium halides involve iron-ate complexes as the active components, whereas reactions of Grignard reagents with two or more carbon atoms are effected by highly reduced iron-clusters of the formal composition [Fe(MgX)2]n generated in situ. Control experiments using the ate-complex [Me4Fe]Li2 corroborate this interpretation.
Addition reactions of cyclic s-trans-enaminones with Grignard reagents
Shawe, Thomas T.,Hansen, Darren B.,Peet, Kelly Ann,Prokopowicz, Anthony S.,Robinson, Patrice M.,Cannon, Annatina,Dougherty, Kathleen E.,Ross, Andrew A.,Landino, Linda M.
, p. 1547 - 1556 (2007/10/03)
Addition of Grignard reagents to s-transenaminones derived from 1,3-cycloalkanediones are described. In dichloromethane, addition of phenylmagnesium bromide gave 3-phenyl substituted cycloalkenones. Alkylmagnesium halides underwent multiple addition reactions, giving mixtures of the 3-alkylcycloalkenones and 1,3-dialkyl-3-(dialkylamino)cyclohexenes. In tetrahydrofuran, only the 3-alkylcycloalkenone was obtained.
New chemistry of cyclic, s-trans-enaminones: Addition of Grignard reagents to enaminones derived from 2-methylcyclohexane-1,3-dione
Shawe, Thomas T.,Landino, Linda M.,Ross, Andrew A.,Prokopowicz, Anthony S.,Robinson, Patrice M.,Cannon, Annatina
, p. 3823 - 3824 (2007/10/03)
Grignard reagents add to cyclic s-trans enaminones to give the cycloalkenone after aqueous hydrolysis. In some cases a competitive double addition takes place. These reactions have been found to be solvent- and reagent-selective.
Reaction of cyclic α-hydroxy epoxides with a strong base: A new 1,2-rearrangement, evidence for a carbenoid pathway
Doris, Eric,Dechoux, Luc,Mioskowski, Charles
, p. 12700 - 12704 (2007/10/03)
Several substituted five- and six-membered cyclic α,β-unsaturated ketones are readily available by treatment of the corresponding α-hydroxy epoxides with an organolithium reagent. The reaction involves a new carbenoid 1,2-alkyl rearrangement. Evidence for the carbenoid intermediate has been obtained by an intramolecular trapping of the highly reactive species.
SYNTHETIC APPLICATIONS OF 2-PHENYLSELENENYLENONES-III AN OVERVIEW
Liotta, Dennis,Saindane, Manohar,Barnum, Christopher,Zima, George
, p. 4881 - 4890 (2007/10/02)
2-Phenylselenenylenones are versatile species which can be selectively converted a number of different ketones and enones in high overall yields.
Reaction of β-halo α,β-unsaturated ketons with cuprate reagents. Efficient syntheses of β,β-dialkyl ketones and β-alkyl α,β-unsaturated ketones. A synthesis of (Z)-jasmone
Piers, Edward,Cheng, Kin Fai,Nagakura, Isao
, p. 1256 - 1263 (2007/10/02)
Treatment of the 3-halo-2-cyclohexen-1-ones 11-15 and 17 with an excess of lithium dimethylcuprate provided good to excellent yields of the corresponding 3,3-dimethylcyclohexanones 21-24.Similar reactions involving the β-bromo cyclopentenones 19 and 20 stopped at the monoaddition stage, producing the cyclopentenones 40 and 43.Reaction of the β-bromo cyclohexenones 12 and 15 with 1.1 equiv. of lithium dimethylcuprate did not effect clean conversion of these substrates into the corresponding 3-methyl-2-cyclohexen-1-ones.When a series of β-bromo enones 12, 14-19were allowed to react with the lithium (phenylthio)(alkyl)cuprates 44-47, the correspondig β-alkyl enones were, in general, produced cleanly and efficiently.However, reaction of 3-bromo-2-methyl-2-cyclopenten-1-one (19) with the cuprate reagent 44 gave mainly the β-phenylthio enone 49.This undesired result could be avoided by employing, in the place of 19, The β-iodo cyclopentenone 50, which reacted smoothly with 44 to give a high yield of 2,3-dimethyl-2-cyclopenten-1-one (40).Reaction of 3-bromo-2-cyclohexen-1-one (14) with 3 equiv. of the mixed vinylcuprate reagent 48 gave 3-(3-butenyl)-2-cyclohexen-1-one (32).Alkylation of 1,3-cyclopentanedione with (Z)-1-chloro-2-pentene afforded compound 51, which was converted into the β-bromo enone 52.Treatment of the latter substance with lithium dimethylcuprate provided (Z)-jasmone (53).
