35998-47-1Relevant articles and documents
A facile 1,2-acetoxychlorination reaction of olefins by using the N,N-dimethtylacetamide/hydrogen chloride/m-chloroperbenzoic acid (or oxone) system
Kim, Hyoung Rae,Oh, Hyun Sook,Park, Hyun Ju,Kim, Jae Nyoung,Jeon, Dong Ju,Ryu, Eung K.
, p. 159 - 165 (1998)
Various alkenes underwent 1,2-acetoxychlorination by dimethylacetamide (DMA)/HCl/m-CPBA (or Oxone) system in good yields.
Intermolecular Halogenation/Esterification of Alkenes with N-Halosuccinimide and Acetic Acid Catalyzed by 1,4-Diazabicyclo[2.2.2]octane
Pimenta, Laura S.,Gusevskaya, Elena V.,Alberto, Eduardo E.
supporting information, p. 2297 - 2303 (2017/07/07)
1,4-Diazabicyclo[2.2.2]octane (DABCO) is a suitable Lewis base that acts as an organocatalyst in the activation of N-chlorosuccinimide (NCS) towards the chlorination of alkenes. The chloriranium ion formed from NCS and the alkene, can be intermolecularly opened by a nucleophile, such as acetic acid, to produce highly functionalized trans-chloro esters in high yields. The protocol is also applied to the synthesis of chlorohydrins and chloro ethers using water or methanol as nucleophiles instead of acetic acid. Brominated analogs can also be synthesized from alkenes and N-bromosuccinimide (NBS) in the presence of various basic catalysts. However, the reaction patterns seem to be remarkably different. The catalytic performance of bases in the bromoesterification of alkenes was found to be strongly affected by their Br?nsted basicity, suggesting that acetyl hypobromite, formed in situ from NBS and acetic acid, acts as a real brominating agent in these systems. (Figure presented.).
Phase-transfer and other types of catalysis with cyclopropenium ions
Bandar, Jeffrey S.,Tanaset, Anont,Lambert, Tristan H.
supporting information, p. 7365 - 7368 (2015/05/13)
Abstract This work establishes the cyclopropenium ion as a viable platform for efficient phase-transfer catalysis of a diverse range of organic transformations. The amenability of these catalysts to large-scale synthesis and structural modification is demonstrated. Evaluation of the molecular structure of an optimal catalyst reveals some unique structural features of these systems. Finally, a discussion of electronic charge distribution underscores an important consideration for catalyst design. Aromatic ions: Tris(dialkylamino)cyclopropenium ions are shown to be effective carbocationic phase-transfer catalysts for a variety of mainstay transformations. The cyclopropenium platform is shown to be modular and accessible on scale. An X-ray structure and electron-density map revealed some unique features of this architecture (see scheme).
Enzymatic preparation of (1S,2R)- and (1R,2S)-stereoisomers of 2-halocycloalkanols
Kolodiazhna, Olga O.,Kolodiazhna, Anastasy O.,Kolodiazhnyi, Oleg I.
, p. 37 - 42 (2013/02/25)
The stereoisomers of cis-2-halocycloalkanols were resolved by a kinetically controlled transesterification with vinyl acetate in the presence of lipases in organic media. High enantioselectivities (ee >98%) and good isolated yields were obtained for all substrates using the appropriate lipase. Burkholderia cepacia lipase was the most efficient enzyme for the resolution of these substrates. The enantiomeric purities of the compounds were defined by derivatization with Mosher's acid and the absolute configurations were determined by chemical correlation.
Convenient synthesis of chlorohydrins from epoxides using zinc oxide: Application to 5,6-epoxysitosterol
Moghaddam, Firouz Matloubi,Saeidian, Hamdollah,Mirjafary, Zohreh,Javan, Marjan Jebeli,Farimani, Mehdi Moridi,Seirafi, Marjan
experimental part, p. 157 - 163 (2009/09/30)
Efficient synthesis of protected and unprotected chlorohydrins has been achieved by ring opening of epoxides with acetyl/benzoyl chloride and TMSCl using a catalytic amount of ZnO as a reusable catalyst. The applicability of ZnO is further extended by performing the cleavage of the natural product 5,6-epoxysitosterol with acetyl chloride.
Conformational properties of trans-2-halo-acetoxycyclohexanes: 1H NMR, solvation and theoretical investigation
Freitas, Matheus P.,Tormena, Cláudio F.,Rittner, Roberto,Abraham, Raymond J.
, p. 211 - 217 (2007/10/03)
Conformational analyses of trans-2-halo-acetoxycyclohexanes have been performed through NMR, theoretical calculations and solvation theory. The solvent dependence of coupling constants analysed together with solvation parameters of the main calculated geo
Trichloroisocyanuric Acid as a Cohalogenating Reagent: An Efficient Transformation of Alkenes into Chlorohydrins, β-Chloroethers and β-Chloroacetates
Mendonca, Gabriela Fonseca,Sanseverino, Antonio Manzolillo,Mattos, Marcio C. S. de
, p. 45 - 48 (2007/10/03)
The preparation of diverse β-chloroethers, β-chloroacetates, and chlorohydrins is efficiently achieved under mild conditions by reaction of alkenes with trichloroisocyanuric acid (0.34 mol equiv) in alcohols (MeOH, EtOH, i-PrOH, t-BuOH), acetic acid or aqueous acetone, respectively.
A one-pot synthesis of β-chloro acetates/benzoates from epoxides
Chandra, Kusum L.,Bisai, Alakesh,Saravanan,Singh, Vinod K.
, p. 221 - 223 (2007/10/03)
A variety of epoxides were converted into β-chloroacetates and benzoates by using TMSCI and the corresponding acid anhydride in the presence of a catalytic amount of Cu(OTf)2.
Organomercury/aluminum-mediated acylative cleavage of cyclic ethers
Luzzio, Frederick A.,Bobb, Rhiana A.
, p. 1851 - 1858 (2007/10/03)
Epoxides and tetrahydrofurans are cleaved with concomitant acylation to chloroalkyl esters using a reagent system composed of an organomercurial, aluminum metal and an acid chloride. The cleavage is promoted under mild conditions by a range of readily-available cyclic β-alkoxychloromercurials and acid chlorides. Using mainly tetrahydrofuran and cyclohexene oxide as substrates, the yield of isolated chloroesters ranged from 52 to 96%.
Addition reactions of nitryl chloride at multiple bonds
Zyk,Bondarenko,Nesterov,Zefirov
, p. 980 - 986 (2007/10/03)
Published data on additio of nitryl chloride to alkenes and possible reaction mechanisms were analyzed. Reactions of nitryl chloride with alkenes differing in the ionization potentials of the double bond and in the abilities to undergo various structural rearrangements were studied. Nitryl chloride was shown to be very sensitive both to the substrate and to the reaction conditions.
