- Synthesis of 3-benzoylcyclohexanone, a key intermediate for the synthesis of ketoprofen
-
A simple and convenient synthesis of 3-benzoylcyclohexanone, a ketoprofen precursor, is proposed. It consists of the preparation of 5-trimethylsilyl-3-cyclohexenone via disilylation of anisole followed by hydrolysis and subsequent regiospecific benzoylati
- Bennetau,Krempp,Dunogues
-
-
Read Online
- Radical hydroalkylation and hydroacylation of alkenes by the use of benzothiazoline under thermal conditions
-
The hydroalkylation and hydroacylation of electrondeficient alkenes proceeded smoothly by using benzothiazoline derivatives as radical-transfer reagents under thermal conditions without light irradiation or any additive. Both benzyl and benzoyl moieties were transferred efficiently.
- Akiyama, Takahiko,Uchikura, Tatsuhiro,Toda, Mitsuhiro,Mouri, Toshiki,Fujii, Tatsuya,Moriyama, Kaworuko,Ibanez, Ignacio
-
p. 12715 - 12723
(2020/11/09)
-
- Benzothiazolines as radical transfer reagents: Hydroalkylation and hydroacylation of alkenes by radical generation under photoirradiation conditions
-
Novel radical transfer reagents under photoirradiation conditions were developed by the use of benzothiazoline derivatives. These reagents enabled both hydroalkylation and hydroacylation of alkenes under neutral conditions at ambient temperature without a
- Uchikura, Tatsuhiro,Moriyama, Kaworuko,Toda, Mitsuhiro,Mouri, Toshiki,Ibá?ez, Ignacio,Akiyama, Takahiko
-
supporting information
p. 11171 - 11174
(2019/09/30)
-
- Visible-Light-Promoted Synthesis of 1,4-Dicarbonyl Compounds via Conjugate Addition of Aroyl Chlorides
-
A facile visible-light photocatalytic conjugate addition to prepare 1,4-dicarbonyl compounds has been developed by employing readily available aroyl chlorides as aryl radical sources. This operationally simple method shows a broad scope with regard to both aroyl chlorides and Michael acceptors. As a result, a variety of 1,4-diketones were efficiently synthesized in moderate to good yields.
- Wang, Chao-Ming,Song, Dan,Xia, Peng-Ju,Wang, Jing,Xiang, Hao-Yue,Yang, Hua
-
supporting information
p. 271 - 274
(2018/01/27)
-
- Direct Aldehyde Csp2?H Functionalization through Visible-Light-Mediated Photoredox Catalysis
-
The development of methods for carbon–carbon bond formation under benign conditions is an ongoing challenge for synthetic chemists. In recent years there has been considerable interest in using selective C?H activation as a direct route for generating rea
- Vu, Minh Duy,Das, Mrinmoy,Liu, Xue-Wei
-
supporting information
p. 15899 - 15902
(2017/11/15)
-
- Synthesis of 3-substituted 2-cyclohexenones through umpoled functionalization
-
A new protocol to obtain 3-substituted 2-cyclohexenones, was developed by reversing the chemical reactivity of 2-cyclohexenone. One-pot synthesis of 3-substituted 2-cyclohexenones can be achieved by treatment of 3-phenylthiosilyl enol ether with a mixture of t-BuLi/HMPA that allows hydrogen-selective exchange in presence of reactive electrophiles such as aldehydes, ketones and alkyl halides. This affords the corresponding product in moderate overall yield, after silyl enol ether cleavage and concomitant thiophenol elimination initiated with TBAF.
- Lechuga-Eduardo, Harim,Zarza-Acu?a, Eduardo,Romero-Ortega, Moisés
-
p. 3234 - 3237
(2017/07/27)
-
- Polymer-supported synthesis of α- and β-hydroxyketones through the formation of 1,3-dithiane intermediates
-
The synthesis of polymer-supported 2-monosubstituted 1,3-dithianes from soluble copolymers bearing 1,3-propanedithiol groups, their lithiation, reactions with electrophiles such as aldehydes, ketones, α,β- unsaturated ketones and oxiranes, and cleavage of
- Bertini, Vincenzo,Lucchesini, Francesco,Pocci, Marco,Alfei, Silvana,Idini, Barbara
-
body text
p. 1141 - 1144
(2009/04/06)
-
- Preparation and Reactions of Diorganozincs from Dienic Silyl Enol Ethers
-
The hydroboration of the dienic silyl enol ethers 1a-d with Et2BH produces organoboranes which are readily converted under mild conditions by a treatment with Et2Zn to the corresponding dialkylzincs 2a-d.These organometallics react after transmetallation with CuCN*2LiCl with various electrophiles affording polyfunctional silyl enol ethers of type 4.In the presence of the chiral catalyst (1R,2R)-bis(trifluoromethanesulfonamido)cyclohexane 6, the dialkylzinc 2b was added to various aldehydes leading to hydroxy silyl enol ethers of type 8 in satisfactory yields (45-77percent) and excellent enantioselectivities (85 to >96percent ee).The chiral products 8 can be oxidatively cyclized using t-BuOOH and catalytic amounts of VO(acac)2 furnishing trisubstituted tetrahydopyrans like 9a,b with high diastereoselectivity.An iodoalkoxylation of 8a affords after HI elimination and Jones oxidation the unsaturated valerolactone 13.
- Devasagayaraj, A.,Schwink, L.,Knochel, P.
-
p. 3311 - 3317
(2007/10/02)
-
- Benzophenone-Mediated Conjugate Additions of Aromatic Aldehydes to Quinones
-
Benzophenone increases the efficiency of the photochemically mediated addition of aldehydes to quinones.
- Kraus, George A.,Liu, Peng
-
p. 7723 - 7726
(2007/10/02)
-
- ACYLSILANE-MEDIATED NUCLEOPHILIC ACYLATION OF α,β-UNSATURATED CARBONYL DERIVATIVES
-
A number of 1,4-diketones and of γ-keto esters can be prepared regiospecifically under mild conditions by employing a TBACN-catalysed Michael addition of acylsilanes to α,β-unsaturated carbonyl derivatives.
- degl'Innocenti, Alessandro,Ricci, Alfredo,Mordini, Alessandro,Reginato, Gianna,Colotta, Vittoria
-
p. 645 - 648
(2007/10/02)
-
- AMINONITRILE AND CYANOHYDRIN ETHERS AS BENZOYL ANION EQUIVALENTS IN CONJUGATE ADDITIONS TO SUBSTITUTED α CYCLENONES : COMPARATIVE SYNTHETIC POTENTIALITIES
-
Lithiated aminonitrile 1a and cyanohydrin ether 2a are good nucleophilic benzoyl equivalents in conjugate addition to α cyclenones. 1a is more sensitive to β substitution of the cyclenone than 2a, as in THF it does not react with 3-methyl substituted cycl
- Zervos, Michel,Wartski, Lya,Seyden-Penne, Jacqueline
-
p. 4963 - 4974
(2007/10/02)
-
- REACTIVITE DE LITHIENS DERIVES D'ETHERS DE LA CYANHYDRINE DU BENZALDEHYDE VIS-A-VIS D'α-ENONES CYCLIQUES
-
Conjugate addition of reagent 1A to 2-cyclohexenone 3 can be realized in THF-HMPT, so that one-pot conjugate addition - CH3I enolate trapping, leading to trans 2-methyl 3-benzoylcyclohexanone 17 can be easily performed.From isophorone 4 and Δ1(9)-2-octalone 5, 1,4-addition under kinetic control is observed in THF.In the presence of HMPA, the reaction is under thermodynamic control.At low temperatures enolate 19a is in equilibrium with 1A and 4; from 4 at 0 deg C or 5 at -65 deg C or at 0 deg C, the equilibrium lies on the side of starting materials.No reaction between 1A and 6 takes place in any solvent.The reaction of 1B and isophorone 4 in THF leads to 1,2-addition under kinetic control and to 1,4-addition under thermodynamic control.In THF-HMPT, retro-Michael addition is observed.However, 1,2-addition takes place in THF to 6. The different results are interpreted in terms of interplay of ion-pairing, steric decompression and steric hindrance to 1,4-addition as well as the possibility of participation of the Li cation for 1,2-addition.
- Seuron, Nadine,Seyden-Penne, Jacqueline
-
p. 635 - 640
(2007/10/02)
-
- ADDITION CONJUGUEE D'AMINONITRILES, EQUIVALENTS DE BENZOYLE, AUX CYCLENONES. QUELQUES EXEMPLES DE SYNTHESES STEREOSELECTIVES DE CYCLANONES 2,3-DISUBSTITUEES CIS.
-
Conjugate addition of benzoyl anion equivalents to unsubstituted and 2-substituted cyclenones is proved in some cases to be highly stereoselective.Cis 2-methyl 3-benzoyl cyclanones are obtained with excellent yields.
- Zervos, M.,Wartski, L.
-
p. 4641 - 4644
(2007/10/02)
-
- THE PREPARATION OF 1,4-DICARBONYL COMPOUNDS BY PHOTOREACTION OF KETONES IN THE PRESENCE OF OXIDANTS
-
Phenyl alkyl ketones were photo-irradiated in the presence of Cr(VI) or Mn(VII) oxidants to yield 1,4-dicarbonyl compounds regiospecifically while 2-octanone gave a regioisomeric mixture of 2,5-, 2,6-, and 2,7-octadiones.
- Mitani, Michiharu,Tamada, Mamoru,Uehara, Shin-ichi,Koyama, Kikuhiko
-
p. 2805 - 2808
(2007/10/02)
-
- ADDITION CONJUGUEE D'EQUIVALENTS D'ACYLES AUX CYCLOHEXEN-2 ONES ET A LA Δ1(9) OCTALONE-2 : SYNTHESE DE DICETONES 1-4.
-
The synthesis of 3-acetylcyclohexanones 11, 12, 13 has been realized by conjugate addition of lithiated cyanohydrin ether 1a to 2-cyclohexanones 2, 3, 4 in THF-HMPA, even if 3-substituted. 3-benzoylcyclohexanones 14, 15, 16 are obtained from 1b and 2, 3,
- Seuron, Nadine,Wartski, Lya,Seyden-Penne, Jacqueline
-
p. 2175 - 2178
(2007/10/02)
-
- Trimethylsilyl Cyanide - A Reagent for Umpolung, III: Nucleophilic Acylation of α,β-Unsaturated Carbonyl Compounds with directed 1,2-/1,4-Additions by Solvent Effects
-
The anion 7 of O-(trimethylsilyl)cyanohydrine 6, derived from benzaldehyde, attacks numerous α-enones in ether exclusively by 1,4-addition, even if C-3 is alkyl-substituted.In THF and DME the 1,2-adduct is formed predominantly; on addition of HMPT or 12-c
- Huenig, Siegfried,Wehner, Gregor
-
p. 302 - 323
(2007/10/02)
-