Demonstration of spontaneous chiral symmetry breaking in asymmetric Mannich and Aldol reactions.

Abstract:

:Spontaneous symmetry breaking in reactive systems, known as a rare physical phenomenon and for the Soai autocatalytic irreversible reaction, might in principle also occur in other, more common asymmetric reactions when the chiral product is capable to promote its formation and an element of "nonlinearity" is involved in the reaction scheme. Such phenomena are long sought after in chemistry as a possible explanation for the biological homochirality of biomolecules. We have investigated homogeneous organic stereoselective Mannich and Aldol reactions, in which the product is capable to form H-bridged complexes with the prochiral educt, and found by applying NMR spectroscopy, HPLC analysis, and optical rotation measurements 0.3-50.8% of random product enantiomeric excess under essentially achiral reaction conditions. These findings imply a hitherto overlooked mechanism for spontaneous symmetry breaking and, hence, a novel approach to the problem of absolute asymmetric synthesis and could have also potential significance for the conundrum of homochirality.

journal_name

Chirality

journal_title

Chirality

authors

Mauksch M,Tsogoeva SB,Wei S,Martynova IM

doi

10.1002/chir.20474

subject

Has Abstract

pub_date

2007-11-01 00:00:00

pages

816-25

issue

10

eissn

0899-0042

issn

1520-636X

journal_volume

19

pub_type

杂志文章
  • Asymmetric Borane Reduction of Prochiral Ketones Catalyzed By Helical Poly[(S)-3-vinyl-2,2'-dihydroxy-1,1'-binaphthyl].

    abstract::The application of helical poly[(S)-3-vinyl-2,2'-dihydroxy-1, 1'-binaphthyl] (L*) in the asymmetric borane reduction of prochiral ketones was studied. The results showed that L* had excellent catalytic activity as well as enantioselectivity, giving up to 96% yield and up to 99% enantiomeric excess (ee) of the correspo...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22459

    authors: Qin G,Chen Y,Yang L,Yang N,Yang Z

    更新日期:2015-07-01 00:00:00

  • Enantioselective separation and degradation of the herbicide dichlorprop methyl in sediment.

    abstract::Chiral pesticides currently constitute about 50% of all pesticides dosage used in China, and this ratio is increasing as more complex structures are introduced. Dichlorprop methyl (DCPPM) is a chiral herbicide consisting of a pair of enantiomers. In this study, the enantiomeric separation of DCPPM was investigated by ...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20624

    authors: Ma Y,Xu C,Wen Y,Liu W

    更新日期:2009-04-01 00:00:00

  • Polymer-Supported Optically Active fac(S)-Tris(thiotato)rhodium(III) Complex for Sulfur-Bridging Reaction With Precious Metal Ions.

    abstract::The optically active mixed-ligand fac(S)-tris(thiolato)rhodium(III) complexes, ΔL -fac(S)-[Rh(aet)2 (L-cys-N,S)](-) (aet = 2-aminoethanethiolate, L-cys = L-cysteinate) () and ΔLL -fac(S)-[Rh(aet)(L-cys-N,S)2 ](2-) were newly prepared by the equatorial preference of the carboxyl group in the coordinated L-cys ligand. T...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22546

    authors: Aizawa S,Tsubosaka S

    更新日期:2016-01-01 00:00:00

  • A stereodynamic fluorescent probe for amino acids. Circular dichroism and circularly polarized luminescence analysis.

    abstract::The use of stereodynamic probes is becoming one of the leading strategies for the fast and effective determination of enantiomeric excess. Recently, we reported a series of novel molecular architectures based on a modified tris(2-pyridylmethyl)amine complex (TPMA), which are able to amplify the electronic CD, in the c...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22780

    authors: Carmo Dos Santos NA,Badetti E,Licini G,Abbate S,Longhi G,Zonta C

    更新日期:2018-01-01 00:00:00

  • Chiral doping of nematic phases and its application to the determination of absolute configuration.

    abstract::Doping nematic liquid crystals with nonracemic chiral compounds induces a twisted nematic (cholesteric) phase. The ability of solutes to twist the nematic phase may be related to the overall shape of the chiral dopant and consequently to its absolute configuration. The cholesteric induction is therefore a powerful too...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20482

    authors: Pieraccini S,Ferrarini A,Spada GP

    更新日期:2008-05-15 00:00:00

  • Parallel kinetic resolution of an oxazolidinone using a quasi-enantiomeric combination of [D,13C]-isotopomers of pentafluorophenyl 2-phenyl propionate.

    abstract::Parallel kinetic resolution of Evans' phenylglycine derived oxazolidinone using an equimolar combination of quasi-enantiomeric active esters (derived from [D,13C]-labeled 2-phenylpropionic acid) was achieved. The levels of stereocontrol were high, leading to products with predictable configurations. ...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20367

    authors: Coumbarides GS,Dingjan M,Eames J,Flinn A,Northen J

    更新日期:2007-05-05 00:00:00

  • On the physical basis of asymmetry and homochirality.

    abstract::Mirror symmetry breaking is ubiquitous in our visible universe taking place in elementary particles, atoms, and molecules. Molecular chirality is not biogenic in itself, although its detection is often considered a biosignature, a conjecture inferred from the fact that we do not know life devoid of homochirality. The ...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22028

    authors: Cintas P,Viedma C

    更新日期:2012-11-01 00:00:00

  • Enantioselectivity in the steady-state pharmacokinetics and transplacental distribution of pindolol at delivery in pregnancy-induced hypertension.

    abstract::Nine patients taking oral doses of 10 mg/12 h rac-pindolol as part of their treatment for hypertension in pregnancy were recruited for the study. Maternal and fetal gestational age ranged from 20-38 years and 28-41 weeks, respectively. Blood was collected from the umbilical cord vein and from the mother from zero to 1...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.10124

    authors: Gonçalves PV,Matthes Ado C,Da Cunha SP,Lanchote VL

    更新日期:2002-08-01 00:00:00

  • Pimarane diterpenes: Natural source, stereochemical configuration, and biological activity.

    abstract::Plants and fungi are seemingly inexhaustible sources of interesting natural products with remarkable structural and biological diversity. One of the most important groups is the terpenes, ubiquitous natural products that are generated by 2 now well-established biosynthetic pathways: the older mevalonate and the more r...

    journal_title:Chirality

    pub_type: 杂志文章,评审

    doi:10.1002/chir.23009

    authors: Reveglia P,Cimmino A,Masi M,Nocera P,Berova N,Ellestad G,Evidente A

    更新日期:2018-10-01 00:00:00

  • Enantioselective disposition of PCB 136 (2,2',3,3',6,6'-hexachlorobiphenyl) in C57BL/6 mice after oral and intraperitoneal administration.

    abstract::Studies of xenobiotic disposition in rodents often employ experimental designs using differing routes of administration. In an effort to investigate the effects of route of administration on enantioselective disposition of xenobiotics, a chiral polychlorinated biphenyl (PCB), racemic PCB 136, was administered as a sin...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20342

    authors: Kania-Korwel I,Shaikh NS,Hornbuckle KC,Robertson LW,Lehmler HJ

    更新日期:2007-01-01 00:00:00

  • Enantioselective Friedel-Crafts reaction of indoles with trifluoroacetaldehyde catalyzed by Cinchona alkaloids.

    abstract::The first direct asymmetric synthetic preparation of trifluoro-1-(indol-3-yl)ethanols (TFIEs) is described by an enantioselective organocatalytic method from indoles and inexpensive trifluoroacetaldehyde methyl hemiacetal. The reaction is catalyzed by hydroquinine to produce TFIEs in an almost quantitative yield and w...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20982

    authors: Borkin DA,Landge SM,Török B

    更新日期:2011-09-01 00:00:00

  • Separation and quantitation of (R)- and (S)-atenolol in human plasma and urine using an alpha 1-AGP column.

    abstract::A method for the determination of (R)- and (S)-atenolol in human plasma and urine is described. The enantiomers of atenolol are extracted into dichloromethane containing 3% heptafluorobutanol followed by acetylation with acetic anhydride at 60 degrees C for 2 h. The acetylated enantiomers were separated on a chiral al...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.530010306

    authors: Enquist M,Hermansson J

    更新日期:1989-01-01 00:00:00

  • Capillary electrophoresis of herbicides. III. Evaluation of octylmaltopyranoside chiral surfactant in the enantiomeric separation of phenoxy acid herbicides.

    abstract::A chiral alkylglucoside surfactant, namely n-octyl-beta-D-maltopyranoside (OM), was evaluated in the enantiomeric separation of phenoxy acid herbicides. The enantiomeric resolution of the phenoxy acid herbicides could be manipulated readily by adjusting the surfactant concentration, ionic strength, pH, the percent org...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/(SICI)1520-636X(1996)8:7<518::AID-CHIR9>3.

    authors: Mechref Y,el Rassi Z

    更新日期:1996-01-01 00:00:00

  • Enantioselective LC/MS method for the determination of an antimalarial agent Fenozan B07 in dog plasma.

    abstract::A chiral liquid chromatography/mass spectrometry (LC/MS) bioanalytical procedure has been developed for the analysis of the antimalaric agent Fenozan B07 in dog plasma. Normal-phase chromatography involving a phenylcarbamate derivative of cellulose coated on silica gel as the chiral stationary phase was used to resolv...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20253

    authors: Maraschiello C,Vilageliu J,Dorronsoro I,Martinez A,Floriano P,Gómez-Acebo E

    更新日期:2006-05-15 00:00:00

  • Photo-ionization spectroscopy and mass spectrometry of some molecular and supramolecular asymmetric systems in the isolated state.

    abstract::Asymmetric molecular and supramolecular systems are characterized by: i. the circular dicroism in the angular distribution of valence photoelectrons emitted from randomly oriented chiral molecules by their interaction with circularly polarized VUV light; ii. the different stability and reactivity of diastereomeric agg...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20274

    authors: Giardini A,Paladini A,Catone D,Piccirillo S,Rondino F,Satta M,Filippi A,Speranza M,Turchini S,Zema N

    更新日期:2006-08-01 00:00:00

  • Stereochemical study of tolperisone, a muscle relaxant agent, by circular dichroism and ultraviolet spectroscopy.

    abstract::The stereochemistry of tolperisone, a chiral aryl-alkyl basic ketone was investigated by means of circular dichroism (CD) and ultraviolet (UV) spectroscopy. The unusually high optical activity of tolperisone hydrochloride in the n-->pi* region is interpreted by the presence of a chiral conformer in solution. For stere...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/1520-636X(2000)12:10<720::AID-CHIR4>3.0.CO

    authors: Zsila F,Hollósi M,Gergely A

    更新日期:2000-11-01 00:00:00

  • Measurements of concentration dependence and enantiomeric purity of terpene solutions as a test of a new commercial VCD spectrometer

    abstract::Vibrational circular dichroism (VCD) spectra of (+)-alpha-pinene solutions in carbon tetrachloride have been measured in the range of volume fractions 5-100% (v/v) in the mid-infrared region. The concentration dependence measured was statistically analyzed with the aim of obtaining a reliable correlation between the V...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/(SICI)1520-636X(2000)12:4<199::AID-CHIR6>3

    authors: Urbanova M,Setnicka V V,Volka K

    更新日期:2000-05-01 00:00:00

  • Synthesis and circular dichroism studies of N,N-bis(2-quinolylmethyl)amino acid Cu(II) complexes: determination of absolute configuration and enantiomeric excess by the exciton coupling method.

    abstract::We report a method to determine the absolute configuration of alpha-amino acids by exciton coupled circular dichroism (ECCD). Naturally occurring amino acids were successfully derivatized with 2-bromomethylquinoline. Complexation of these conformationally flexible ligands with Cu(II) salts yielded defined propeller-li...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.10079

    authors: Holmes AE,Zahn S,Canary JW

    更新日期:2002-06-01 00:00:00

  • Chiral separation and CD characterisation of enantiomeric cyclotriphosphazene derivatives.

    abstract::The gem-disubstituted cyclotriphosphazene 1 reacted with piperazine (pip) to give the piperazine-bridged derivative 2, which is expected to exist in meso and racemic forms because the two PCl (pip) groups are stereogenic. The proton-decoupled (31)P NMR spectrum of 2 gave rise to two similar sets of ABX signals in a 1:...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20187

    authors: Bui TT,Coles SJ,Davies DB,Drake AF,Eaton RJ,Hursthouse MB,Kiliç A,Shaw RA,Yeşilot S

    更新日期:2005-10-01 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

  • The possible role of enantiodiscrimination in bilirubin toxicity.

    abstract::The possibility that enantiodiscrimination of bilirubin might be involved in neuronal membrane destabilization, and therefore in bilirubin toxicity, was investigated, by circular dichroism, on model membranes composed of phospholipids. The equilibrium between bilirubin enantiomers is displaced at some extent by the in...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20610

    authors: Bernardini C,D'Arrigo P,Elemento G,Mancini G,Servi S,Sorrenti A

    更新日期:2009-01-01 00:00:00

  • Research into the oxidation of abietic acid-derived enone with atmospheric oxygen.

    abstract::This work presents results of methyl 7-oxoabiet-13(14)-en-18-oate (3) self-oxidation with air-oxygen in the presence of various bases such as triethylamine or sodium t-butoxide. While under aerobic conditions, the use of sodium t-butoxide as a base results in the formation of four isomeric alcohols, an addition of tri...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.23176

    authors: Masnyk M,Kuśmirek D,Trzybiński D,Frelek J

    更新日期:2020-04-01 00:00:00

  • Absolute structural elucidation of natural products--a focus on quantum-mechanical calculations of solid-state CD spectra.

    abstract::In this review article we examine state-of-the-art techniques for the structural elucidation of organic compounds isolated from natural sources. In particular, we focus on the determination of absolute configuration (AC), perhaps the most challenging but inevitable step in the whole process, especially when newly isol...

    journal_title:Chirality

    pub_type: 杂志文章,评审

    doi:10.1002/chir.20795

    authors: Pescitelli G,Kurtán T,Flörke U,Krohn K

    更新日期:2009-01-01 00:00:00

  • Liquid chromatographic resolution of 3-amino-1,4-benzodiazepin-2-one derivatives on various Pirkle-type chiral stationary phases.

    abstract::The two enantiomers of N-acyl amide and N-ureide derivatives of 3-amino-5-phenyl-1,4-benzodiazepin-2-ones, which have been known to show anti-respiratory syncytial virus (RSV) activity, were resolved on seven different Pirkle-type chiral stationary phases (CSPs) with the use of 10% isopropyl alcohol in hexane as a mob...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20944

    authors: Park JY,Cho HS,Hyun MH

    更新日期:2011-01-01 00:00:00

  • Three-Dimensional Chemical Structure Search Using the Conformational Code for Organic Molecules (CCOM) Program.

    abstract::Searching the 3D structural fragments of organic molecules is challenging because of structural differences between X-ray and theoretically calculated geometries and the conformational flexibility of substituents. The codification program called Conformational Code for Organic Molecules (CCOM) can be used to unambiguo...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22596

    authors: Izumi H,Nafie LA,Dukor RK

    更新日期:2016-05-01 00:00:00

  • Absolute configuration and enantiodifferentiation of a hemicryptophane incorporating an azaphosphatrane moiety.

    abstract::The hemicryptophane racemate (±)-1 was optically resolved by semipreparative HPLC on Chiralpak IC column. The absolute configuration of each isolated enantiomer was established from the analysis of their electronic circular dichroism spectra. Enantiodifferentiation of the chiral cationic cage (±)-1 was evidenced in so...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22100

    authors: Payet E,Dimitrov-Raytchev P,Chatelet B,Guy L,Grass S,Lacour J,Dutasta JP,Martinez A

    更新日期:2012-12-01 00:00:00

  • Chemoenzymatic and microbial dynamic kinetic resolutions.

    abstract::This review tracks a decade of dynamic kinetic resolution developments with a biocatalytic inclination using enzymatic/microbial means for the resolution part followed by the racemization reactions either by means of enzymatic or chemocatalyst. These fast developments are due to the ability of the biocatalysts to sign...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.20619

    authors: Kamaruddin AH,Uzir MH,Aboul-Enein HY,Halim HN

    更新日期:2009-04-01 00:00:00

  • Noncovalent immobilization of ionic-tagged box-Cu(OAc)2 complex and its application in asymmetric Henry reaction.

    abstract::Immobilized Cu(OAc)(2)-bis(oxazolines) via hydrogen bonding by SBA-15 was applied to asymmetric Henry reaction, and good enantioselectivities were obtained (up to 83% ee) between 2-methoxybenzaldehyde and CH(3)NO(2) in isopropyl alcohol (iPrOH). The catalyst could be reused seven times without any obvious loss in enan...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22104

    authors: Li ZH,Zhou ZM,Hao XY,Zhang J,Dong X,Liu YQ

    更新日期:2012-12-01 00:00:00

  • Excavations in drug chirality: 1. Cyclothiazide.

    abstract::There is a great deal of current interest in the role and importance of chirality in the development of new drugs, but little attention is being paid to the stereochemistry of older drugs. Indeed, many older chiral drugs were introduced without adequate information on their stereochemical identity or composition. We h...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.530030103

    authors: Nusser E,Banerjee A,Gal J

    更新日期:1991-01-01 00:00:00

  • Stereolability of chiral ruthenium catalysts with frozen NHC ligand conformations investigated by dynamic-HPLC.

    abstract::The stereolability of chiral Hoveyda-Grubbs II type ruthenium complexes bearing N-heterocyclic carbene (NHC) ligands with Syn-phenyl groups on the backbone and Syn- or Anti-oriented o-tolyl N-substituents was studied by resorting to dynamic high-performance liquid chromatography (D-HPLC). A complete chromatographic pi...

    journal_title:Chirality

    pub_type: 杂志文章

    doi:10.1002/chir.22487

    authors: Menta S,Pierini M,Cirilli R,Grisi F,Perfetto A,Ciogli A

    更新日期:2015-10-01 00:00:00