Organocatalytic aza-Michael/retro-aza-Michael reaction: pronounced chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction.

Abstract:

:A detailed experimental investigation of an aza-Michael reaction of aniline and chalcone is presented. A series of Cinchona alkaloid-derived organocatalysts with different functional groups were prepared and used in the aza-Michael and retro-aza-Michael reaction. There was an interesting finding that a complete reversal of stereoselectivity when a benzoyl group was introduced to the cinchonine and cinchonidine. The chirality amplification vs. time proceeds in the quinine-derived organocatalyst containing silicon-based bulky group, QN-TBS, -catalyzed aza-Michael reaction under solvent-free conditions. In addition, we have demonstrated for the first time that racemization was occurred in suitable solvents under mild conditions due to retro-aza-Michael reaction of the Michael adduct of aniline with chalcone. These indicate the equilibrium of retro-aza-Michael reaction and aza-Michael reaction produce the happening of chirality amplification in aza-Michael reaction and racemization via retro-aza-Michael reaction under different conditions, which would be beneficial to the development of novel chiral catalysts for the aza-Michael reactions.

journal_name

Chirality

journal_title

Chirality

authors

Cai YF,Li L,Luo MX,Yang KF,Lai GQ,Jiang JX,Xu LW

doi

10.1002/chir.20940

subject

Has Abstract

pub_date

2011-05-01 00:00:00

pages

397-403

issue

5

eissn

0899-0042

issn

1520-636X

journal_volume

23

pub_type

杂志文章
  • Chiral memory: induction, amplification, and switching in porphyrin assemblies.

    abstract::The interaction between the tetra-anionic porphyrin H2TPPS and its copper derivative, CuTPPS, with the tetra-cationic porphyrin H2T4 and its copper derivative, CuT4, leads, in aqueous solution, to the formation of remarkably stable and kinetically inert heteroaggregates. The aggregation process is under hierarchic con...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20464

    authors: Rosaria L,D'urso A,Mammana A,Purrello R

    更新日期:2008-03-01 00:00:00

  • Discrimination of chiral guests by chiral channels: variable temperature studies by SXRD and solid state 13C NMR of the deoxycholic acid complexes of camphorquinone and endo-3-bromocamphor.

    abstract::3alpha,12alpha-dihydroxy-5beta-cholan-24-oic acid (deoxycholic acid DCA) is able to discriminate between the R- and S-enantiomers of camphorquinone and endo-(+)-3-bromocamphor and select only the S-enantiomers from a racemic mixture. DCA forms novel well ordered 1:1 adducts with (1S)-(+)-camphorquinone and (1S)-endo-(...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20561

    authors: Tahir MI,Rees NH,Heyes SJ,Cowley AR,Prout K

    更新日期:2008-07-01 00:00:00

  • Determination of the absolute configuration and solution conformation of a novel disubstituted pyrrolidine acid A by vibrational circular dichroism.

    abstract::Compound A, a novel disubstituted pyrrolidine acid, is a member of a new class of agents that are potentially useful for the treatment of diabetes and dyslipidemia. The absolute configuration of this compound was determined by using vibrational circular dichroism (VCD). The results are in agreement with the assignment...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20316

    authors: Freedman TB,Cao X,Phillips LM,Cheng PT,Dalterio R,Shu YZ,Zhang H,Zhao N,Shukla RB,Tymiak A,Gozo SK,Nafie LA,Gougoutas JZ

    更新日期:2006-09-01 00:00:00

  • Catalytic asymmetric synthesis of 19,20-dihydroakuammicine.

    abstract::An enantiocontrolled total synthesis of 19,20-dihydroakuammicine using a catalytic asymmetric Michael addition of dimethyl malonate to cyclohexenone as the key step is described. The above catalytic asymmetric Michael addition proceeds quite efficiently in the presence of a heterobimetalic asymmetric catalyst (ALB-KO-...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/(SICI)1520-636X(2000)12:5/6<400::AID-CHIR1

    authors: Ohori K,Shimizu S,Ohshima T,Shibasaki M

    更新日期:2000-06-01 00:00:00

  • Metabolic chiral inversion of ibuprofen in isolated rat hepatocytes.

    abstract::Ibuprofen was used to demonstrate that isolated rat hepatocytes offer a suitable in vitro model to investigate the metabolic chiral inversion of anti-inflammatory 2-arylpropionic acids (profens). The inversion of the pharmacologically inactive (-)-(R)-ibuprofen to the active (+)-(S)-ibuprofen was shown to obey apparen...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.530020203

    authors: Müller S,Mayer JM,Etter JC,Testa B

    更新日期:1990-01-01 00:00:00

  • Base-catalyzed epimerization of the butenolide in annonaceous acetogenins.

    abstract::The elusive epimerization process in the chiral butenolide moiety of Annonaceous acetogenins was examined under several sets of conditions commonly used for elimination leading to the alpha, beta-unsaturated lactone and the results provide practical guidance in choosing elimination conditions. ...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/(SICI)1520-636X(2000)12:3<127::AID-CHIR4>3

    authors: Yu Q,Wu Y,Wu YL,Xia LJ,Tang MH

    更新日期:2000-03-01 00:00:00

  • Spectroscopic studies on nicotine and nornicotine in the UV region.

    abstract::The UV absorption and electronic circular dichroism (ECD) spectra of (R)- and (S)-nicotine and (S)-nornicotine in aqueous solution were measured to a significantly lower wavelength range than previously reported, allowing the identification of four previously unobserved electronic transitions. The ECD spectra of the t...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22141

    authors: Clayton PM,Vas CA,Bui TT,Drake AF,McAdam K

    更新日期:2013-05-01 00:00:00

  • The so-called "interconversion" of stereoisomeric drugs: an attempt at clarification.

    abstract::A variety of reactions can be categorized under the global concept of the "interconversion of stereoisomers." Thus, racemization or epimerization can result from inversion of labile chiral centers. From the examples available, some predictive rules are suggested for a chiral center of the type R"R'RC-H undergoing base...

    journal_title:Chirality

    pub_type: 杂志文章,评审

    doi:10.1002/chir.530050302

    authors: Testa B,Carrupt PA,Gal J

    更新日期:1993-01-01 00:00:00

  • Programmed assembly of rigid-rod beta-barrel pores: thermal inversion of chirality.

    abstract::The programmed assembly of p-octiphenyl rods carrying six complementary tripeptide strands was studied in the presence of bilayer membranes using circular dichroism (CD) spectroscopy. Thermal CD experiments demonstrated programmed assembly of anionic and cationic rods into supramolecules at low temperature that irreve...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20034

    authors: Sakai N,Matile S

    更新日期:2004-01-01 00:00:00

  • Absolute configuration of oplopanone derivatives from Serphidium stenocephalum: ECD spectra of acyclic ketones with front-octant contributions.

    abstract::The electronic circular dichroism (ECD) spectra of two sesquiterpenoids (1 and 2) related to oplopanone, obtained from a methanolic extract of the plant Serphidium stenocephalum (Artemisia stenocephala), were measured and reproduced by means of time-dependent density functional theory (TDDFT) calculations, establishin...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22263

    authors: Shafiq N,Saleem M,Riaz N,Tousif MI,Jabbar A,Tareen RB,Pescitelli G

    更新日期:2014-01-01 00:00:00

  • Optically active α-phenylethylamine as efficient organocatalyst in the solvent-free reactions between 2,3-butanedione and conjugated nitroolefins.

    abstract::(R)-(+) and (S)-(-)-1-phenylethylamine have been shown to promote highly diastereoselective and complementary enantioselective formal [3 + 2]carbocyclization reactions between 2,3-butanedione and conjugated nitroalkenes with formation of enantiomerically rich 2-hydroxy-3-nitrocyclopentanone derivatives. The reactions ...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22088

    authors: Felluga F,Forzato C,Nitti P,Pitacco G,Prati F,Valentin E,Zangrando E

    更新日期:2012-12-01 00:00:00

  • Spectroscopic properties of the nonplanar amide group: a computational study.

    abstract::Experimental studies suggest that amide bond may significantly deviate from planar arrangement even in linear peptides and proteins. In order to find out the extent to which such deviation may influence principal amide spectroscopic properties, we conducted a computational study of nonplanar N-methylacetamide (NMA) co...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20462

    authors: Bednárová L,Malon P,Bour P

    更新日期:2007-11-01 00:00:00

  • Enantioseparation and determination of flumequine enantiomers in multiple food matrices with chiral liquid chromatography coupled with tandem mass spectrometry.

    abstract::The present work firstly described the enantioseparation and determination of flumequine enantiomers in milk, yogurt, chicken, beef, egg, and honey samples by chiral liquid chromatography-tandem mass spectrometry. The enantioseparation was performed under reversed-phase conditions on a Chiralpak IC column at 20°C. The...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.23125

    authors: Li S,Liu B,Xue M,Yu J,Guo X

    更新日期:2019-11-01 00:00:00

  • Steady-state pharmacokinetics of indobufen enantiomers in patients with obliterative atherosclerosis.

    abstract::Steady-state pharmacokinetics of indobufen (INDB) enantiomers administered as racemic INDB (rac-INDB) tablets and bleeding time were studied in patients. Two-hundred mg INDB tablets (Ibustrin) were administered twice daily for 7 days to obliterative atherosclerosis patients. Enantiospecific reversed phase (RP) HPLC wi...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.1036

    authors: Glówka FK,Strzelecka D,Zapalski S

    更新日期:2001-06-01 00:00:00

  • Synthesis of epimers of L-cyclopentenylglycine using enzymatic resolution.

    abstract::Both epimers of the naturally occurring nonproteinogenic amino acid L-cyclopentenylglycine, (2S,1'S)- and (2S, 1'R)-2-(cyclopent-2'-enyl)glycine, were obtained via a procedure involving condensation of 3-chlorocyclopentene with diethyl acetylaminomalonate, deethoxycarbonylation, chromatographic separation of the resul...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/1520-636X(2000)12:9<665::AID-CHIR4>3.0.CO;

    authors: Andersen L,Nielsen B,Jaroszewski JW

    更新日期:2000-10-01 00:00:00

  • Stereoselective chiral inversion of pantoprazole enantiomers after separate doses to rats.

    abstract::(+/-)-Pantoprazole ((+/-)-PAN), (+/-)-5-(difluoromethoxy)-2-[[3.4-dimethoxy-2-pyridinyl)methyl]sul finyl]- 1H-benzimidazole) is a chiral sulfoxide that is used clinically as a racemic mixture. The disposition kinetics of (+)-PAN and (-)-PAN given separately has been studied in rats. Serum levels of (+)- and (-)-PAN an...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/(SICI)1520-636X(1998)10:8<747::AID-CHIR5>3

    authors: Masubuchi N,Yamazaki H,Tanaka M

    更新日期:1998-01-01 00:00:00

  • Plasmonic nanoparticles assemblies templated by helical bacteria and resulting optical activity.

    abstract::Plasmonic nanoparticles (NPs) adsorbing onto helical bacteria can lead to formation of NP helicoids with micron scale pitch. Associated chiroptical effects can be utilized as bioanalytical tool for bacterial detection and better understanding of the spectral behavior of helical self-assembled structures with different...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.23225

    authors: Feng W,Kadiyala U,Yan J,Wang Y,DiRita VJ,VanEpps JS,Kotov NA

    更新日期:2020-07-01 00:00:00

  • Variable stereochemistry in highly branched isoprenoids from diatoms.

    abstract::C(25) highly branched isoprenoid (HBI) alkenes are ubiquitous lipids found in geochemical samples around the globe. The origins of these widespread geochemicals are believed to be restricted to a limited number of diatoms, including Haslea ostrearia (and related species), Rhizosolenia setigera, and Pleurosigma interme...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.1053

    authors: Belt ST,Allard WG,Johns L,König WA,Massé G,Robert JM,Rowland S

    更新日期:2001-08-01 00:00:00

  • Role of the weak interactions in enantiorecognition of racemic dihydropyrimidinones by novel brush-type chiral stationary phases.

    abstract::The chiral discrimination ability of two recently prepared chiral stationary phases (CSP 1 and CSP 2), based on a leucine derived chiral selector, was tested for the enantiomers of dihydropyrimidone (DHPM) derivatives and compared with the commercially available Hyun-leucine CSP 3 and classical Pirkle-leucine CSP 4. B...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20396

    authors: Forjan DM,Gazić I,Vinković V

    更新日期:2007-06-01 00:00:00

  • Enantioselective LC/ESI-MS/MS analysis and pharmacokinetic and tissue distribution study of (2RS)-1-(7-methoxy-1H-indol-4-yloxy)-3-(2-(2-methoxyphenoxy)ethylamino)-propan-2-ol in rats.

    abstract::A sensitive and stereospecific liquid chromatography-tandem mass spectrometry method for the quantitative determination of TWo8 enantiomers ((2RS)-1-(7-methoxy-1H-indol-4-yloxy)-3-(2-(2-methoxyphenoxy)ethylamino)-propan-2-ol) was developed and validated in rat serum and some tissues. Racemic TWo8 is a new chemical ent...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22011

    authors: Walczak M,Szymura-Oleksia J,Groszek G

    更新日期:2012-08-01 00:00:00

  • Highly diastereoselective addition of silyldihalomethyllithiums to chiral alkyl esters.

    abstract::Treatment of benzoate, formate, or trifluoroacetate esters with silyldibromomethyllithiums provides alkyl silyl mixed acetals via the 1,3-rearrangement of a silyl group from carbon to oxygen. A high level of asymmetric induction onto the acetal carbon is observed when chiral alkyl esters are employed. The stereochemic...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.10152

    authors: Shinokubo H,Kondo J,Inoue A,Oshima K

    更新日期:2003-01-01 00:00:00

  • The biological activities of prothioconazole enantiomers and their toxicity assessment on aquatic organisms.

    abstract::Chiral fungicide prothioconazole has a wide range of antifungal spectrum; however, little research has been conducted to evaluate prothioconazole on an enantiomeric level. Five target pathogens and three common aquatic organisms were tested for the enantioselective bioactivity and toxicity of prothioconazole in this w...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.23075

    authors: Zhai W,Zhang L,Cui J,Wei Y,Wang P,Liu D,Zhou Z

    更新日期:2019-06-01 00:00:00

  • Circular dichroism eigenspectra of polyproline II and β-strand conformers of trialanine in water: Singular value decomposition analysis.

    abstract::Despite that a number of experimental and theoretical investigations have been carried out to determine the structure of trialanine in water, the reported populations of polyproline II (PPII) and β-strand conformers vary and were found to be dependent on which spectroscopic method was used. Such discrepancies are due ...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20870

    authors: Oh KI,Lee KK,Park EK,Yoo DG,Hwang GS,Cho M

    更新日期:2010-01-01 00:00:00

  • Enantioseparation of flurbiprofen enantiomers using chiral ionic liquids by liquid-liquid extraction.

    abstract::Flurbiprofen is a kind of nonsteroidal anti-inflammatory drug, which has been widely used in clinic for treatment of rheumatoid arthritis and osteoarthritis. It has been reported that S-flurbiprofen shows good performance on clinic anti-inflammatory treatment, while R-enantiomer almost has no pharmacological activitie...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.23071

    authors: Cui X,Ding Q,Shan RN,He CH,Wu KJ

    更新日期:2019-06-01 00:00:00

  • Plant and soil enantioselective biodegradation of racemic phenoxyalkanoic herbicides.

    abstract::The biodegradation of the chiral phenoxyalkanoic herbicides 2-(2,4-dichlorophenoxy)propionic aid (2,4-DP) and 2-(4-chloro-2-methylphenoxy)propionic acid (MCPP) was investigated using enantioselective HPLC and chiroptical detection. Racemic mixtures of 2,4-DP and MCPP were applied to three species of turf grass, four s...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/(SICI)1520-636X(1999)11:4<330::AID-CHIR12>

    authors: Schneiderheinze JM,Armstrong DW,Berthod A

    更新日期:1999-01-01 00:00:00

  • Chiral discrimination by albumin: a mechanistic study of liquid chromatographic optical resolution of nonaromatic carboxylic acids.

    abstract::In order to get further insight into the mechanism by which bovine serum albumin (BSA) discriminates between enantiomers of organic acids, some radioisotopically labeled, nonaromatic carboxylic acids were studied under varying mobile phase conditions. It was found for a series of N-alkanoyl-DL-[3H]leucines that the D-...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.530050503

    authors: Allenmark S

    更新日期:1993-01-01 00:00:00

  • Separation of Enantiomers of a Phospholipid in Langmuir Monolayers by a New Selector.

    abstract::Chiral discrimination in a racemic mixture of dipalmitoylphosphatidylcholine (DPPC) is induced by a new selector at the water-air interface: L-DPPC is segregated in the condensed phase of a Langmuir monolayer upon interactions with an enantiopure amphiphilic compound. ...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22508

    authors: Caminati G,Cicchi S,Lascialfari L,Brandi A

    更新日期:2015-11-01 00:00:00

  • Successful use of a novel lux® i-Amylose-1 chiral column for enantioseparation of "legal highs" by HPLC.

    abstract::Bath salts, fumigations, cleaners and air fresheners, behind these terms substances are hidden, which count as "Legal Highs". These fancy names are used to pretend Legal Highs as harmless compounds, to circumvent legal regulations for marketing as well as to increase the sales. Besides classic illicit drugs of synthet...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.23135

    authors: Kadkhodaei K,Kadisch M,Schmid MG

    更新日期:2020-01-01 00:00:00

  • (R,R)-N,N'-dimethylcyclohexyl-1,2-diazaseleno-phospholidine as a chiral derivatizing agent for the evaluation of chiral alcohols.

    abstract::Previously, a diazaphospholidine has been synthesized and evaluated as a chiral derivatizing reagent for the determination of the optical purity of chiral alcohols via 31P NMR spectroscopy (Alexakis et al., J. Org. Chem. 57:1224-1237, 1992). Our laboratory is interested in the advantageous and practical applications o...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.530060306

    authors: House KL,O'Connor MJ,Silks LA 3rd,Dunlap RB,Odom JD

    更新日期:1994-01-01 00:00:00

  • Synthesis of a new enantiomerically pure P-chiral phosphine and its use in probing the mechanism of the Mitsunobu reaction.

    abstract::A new enantiomerically pure P-chiral phosphine, (S)-cyclohexylmethyl- (1-naphthyl)phosphine (1) was prepared by phosphine-borane methodology and used in a mechanistic study of the Mitsunobu reaction. Enantiomerically enriched (S)-cyclo- hexylmethyl(1-naphtyl)phosphine oxide (8) is obtained if the reaction proceeds thr...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/(SICI)1520-636X(2000)12:5/6<346::AID-CHIR8

    authors: Watanabe T,Gridnev ID,Imamoto T

    更新日期:2000-06-01 00:00:00