α,β‐Unsaturated Aldehydes as Substrates for Asymmetric CC Bond Forming Reactions with Thiamin Diphosphate (ThDP)‐Dependent Enzymes

Cosp, Anabel; Dresen, Carola; Pohl, Martina; Walter, Lydia; Röhr, Caroline; Müller, Michael

doi:10.1002/adsc.200700550

Cited by 46 publications

(42 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…For example, in previous studies we have noted that 2,3-alkanediones are frequently present in aeration samples that contain 3-hydroxyalkan-2-ones ). Although both (E)-2-hydroxy-4-octen-3-one and (E)-3-hydroxy-4-octen-2-one have been reported as synthetic products from enzyme-catalyzed reactions of α,β-unsaturated aldehydes with aldehydes (Cosp et al 2008), to our knowledge, neither has been identified from natural sources before.…”

Section: Discussionmentioning

confidence: 97%

“…1 H NMR δ 7.02 (dt, J=15.6, 7.0 Hz, 1H), 6.20 (dt, J=16.0, 1.6 Hz, 1H), 4.42 (dq, J=7.0, 5.6 Hz, 1H), 3.63 (d, J=5.2 Hz, 1H), m (2.25-2.19, 2H), m (1.55-1.46, 2H), 1.35 (d, J=6.8 Hz, 3H), 0.93 (t, J=7.2 Hz, 3H). The 1 H NMR spectrum was in agreement with that previously reported (Cosp et al 2008). The enantiomers were separated by 0.8 min on the Cyclodex B GC column.…”

Section: Sources Of Chemicalsmentioning

confidence: 96%

“…The reaction mixture was extracted with Et 2 O, and the ether extract was washed with saturated Na 2 CO 3 , water, and brine. The organic layer was dried over anhydrous Na 2 SO 4 and concentrated, and the crude product was purified by flash chromatography (hexanes/EtOAc=9/1) to give 10 as a colorless oil (22 mg (Cosp et al 2008).…”

Section: Sources Of Chemicalsmentioning

confidence: 99%

See 2 more Smart Citations

(2S,4E)-2-Hydroxy-4-octen-3-one, a Male-Produced Attractant Pheromone of the Cerambycid Beetle Tylonotus bimaculatus

et al. 2015

View full text Add to dashboard Cite

We report the identification of a novel pheromone structure from males of the cerambycid beetle Tylonotus bimaculatus Haldeman (Cerambycinae: Hesperophanini), a species native to eastern North America. Volatiles collected from adult males contained (2S,4E)-2-hydroxyoct-4-en-3-one (71%), (3R,4E)-3-hydroxyoct-4-en-2-one (15%), (E)-4-octen-2,3-dione (13%), and 2,3-octanedione (1.5%). Four independent field bioassays with synthetic compounds confirmed that adults of both sexes were attracted by the racemate of the major component, (E)-2-hydroxyoct-4-en-3-one. No other cerambycid species were attracted in significant numbers. Attraction of both sexes is consistent with the male-produced pheromones of many other species in the subfamily Cerambycinae, but T. bimaculatus is unusual in having a pheromone chemistry that is so far unique among species in that subfamily.

show abstract

Section: Discussionmentioning

confidence: 97%

Section: Sources Of Chemicalsmentioning

confidence: 96%

See 1 more Smart Citation

(2S,4E)-2-Hydroxy-4-octen-3-one, a Male-Produced Attractant Pheromone of the Cerambycid Beetle Tylonotus bimaculatus

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Beispielhaft sollen hier drei Enzyme ausführlicher besprochen werden: die Pyruvatdecarboxylase (PDC) aus Zymomonas mobilis [6,7], die Benzaldehydlyase (BAL) aus P. fluorescens [8][9][10][11][12][13][14] und die verzweigtkettige Ketosäuredecarboxylase (KdcA) aus Lactococcus lactis [15,16].…”

Section: Ergebnisseunclassified

“…Es wurde wegen seiner leichten Zugänglichkeit, der höheren Stabilität und insbesondere aufgrund der Möglichkeit, die Synthese von (R)-Phenylacetylcarbinol (PAC) ausgehend von den Aldehyden Acetaldehyd und Benzaldehyd zu katalysieren, ausgewählt. Letzteres steht im Gegensatz zur PDC aus Hefe, die Ketosäuren wie Pyruvat als Ausgangsverbindung für die intrinsische Herstellung des Acetaldehyds benötigt [14]. Allerdings ist das bakterielle Enzym hinsichtlich seiner C-C-Verknüpfungs-aktivität weniger aktiv als das Enzym der Hefe.…”

Section: R-selektive Enzymeunclassified

Entwicklung einer Enzymplattform für die biokatalytische C–C‐Verknüpfung

Pohl

Gocke

Müller

et al. 2010

Chemie Ingenieur Technik

View full text Add to dashboard Cite

Enzyme‐Catalyzed Asymmetric Synthesis

Gröger

2010

Catalytic Asymmetric Synthesis

View full text Add to dashboard Cite

INTRODUCTIONBiocatalysis has been recognized over the past decades as a highly valuable tool for organic chemists to prepare enantiomerically pure molecules, so -called chiral building blocks, in a highly effi cient way. Besides a multitude of academic work, it is noteworthy that enzyme catalysis belongs to the standard repertoire in industry when facing challenging enantioselective synthetic routes. A broad range of biocatalytic methods is already in use in particular for large -scale manufacture of drug intermediates [1] .The research in the fi eld of enzyme catalysis has already been comprehensively reviewed some years ago [2] . Thus, the focus of the current review is on a selection of (particularly recently developed) enantioselective enzymatic reactions, which turned out to be highly useful and applicable in organic synthesis, fulfi lling criteria such as high productivity, substrate concentrations, conversions, and enantioselectivities. The presented methods are an interesting complementary tool to existing " classic organic " or " chemocatalytic asymmetric " methodologies. Among biocatalytic reactions, both resolution of racemates and asymmetric synthesis starting from prochiral substrates are attractive routes already applied, in part, in industry. A third type of biotechnological approach, which is not a subject of this review, are fermentation processes. A graphical summary of these three types of so -called " white biotechnology " methodologies is given in Scheme 6.1 .Hydrolases are the enzyme class most commonly applied as biocatalysts in organic chemistry. This is mainly due to the accessibility of these enzymes (used, e.g., in the textile and detergents industry), their suitability for transformations in organic media Catalytic Asymmetric Synthesis, Third Edition, Edited by Iwao Ojima 269 270 ENZYME-CATALYZED ASYMMETRIC SYNTHESIS (in particular when using lipases), and the lack of a need for cofactors. However, in recent years, we have also seen an increasing tendency to apply redox enzymes in organic syntheses as well as lyases in C -C bond formations and transferases. Isomerases also turned out to be very useful in particular in combination with hydrolases for dynamic kinetic resolutions. Thus, a broad range of biotransformations is available for organic chemists. A challenge, however, is the use of ATP cofactor -dependent enzymes, which contribute to only a negligible number of typical organic biotransformations (e.g., due to the high price of ATP).The fi eld of biocatalysis benefi ted signifi cantly from the tremendous progress in molecular biology. Highly effi cient methods for screening and optimization of biocatalysts (by, e.g., directed evolution in the latter case) have been developed, which allows access to tailor -made enzymes. Furthermore, the design of recombinant microorganisms gives access to highly productive whole -cell catalysts, which contain only the desired enzymes in large amount, thus signifi cantly reducing the required biomass for biotransformations compared with the use of...

show abstract

α,β‐Unsaturated Aldehydes as Substrates for Asymmetric CC Bond Forming Reactions with Thiamin Diphosphate (ThDP)‐Dependent Enzymes

Cited by 46 publications

References 56 publications

(2S,4E)-2-Hydroxy-4-octen-3-one, a Male-Produced Attractant Pheromone of the Cerambycid Beetle Tylonotus bimaculatus

(2S,4E)-2-Hydroxy-4-octen-3-one, a Male-Produced Attractant Pheromone of the Cerambycid Beetle Tylonotus bimaculatus

Entwicklung einer Enzymplattform für die biokatalytische C–C‐Verknüpfung

Enzyme‐Catalyzed Asymmetric Synthesis

Contact Info

Product

Resources

About