Chapter 9 Pyridoxal phosphate-dependent enzymic reactions: mechanism and stereochemistry

Akhtar, Muhammad; Emery, Vincent

doi:10.1016/s0167-7306(08)60380-4

Cited by 8 publications

(6 citation statements)

References 174 publications

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“…1981b) to operate with inversion of configuration, in direct contrast to other PLP-dependent -decarboxylases for which the stereochemistry of reaction has been determined. In all other cases examined, the reaction proceeds with retention of configuration-that is, the incoming proton occupies the same stereochemical position as did the departing carboxyl group (Dunathan, 1971;Snell, 1982;Floss & Vederas, 1982;Akhtar et al, 1984; Palcic & Floss, 1985; Nakazawa et al, 1981 & Gould, 1982; Orr et al, 1984;Wigle et al, 1982;Robins, 1983;Asada et al, 1984). In view of the observation that many other types of PLP enzymatic reactions occur on a single face of the substrate-cofactor complex [Liu et al (1984) and references cited therein], it appeared important to confirm the unique B. sphaericus decarboxylase results and to determine whether the corresponding enzyme from eukaryotic sources like wheat germ behaves similarly.…”

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confidence: 98%

“…Determination of the stereochemical course of PLP-dependent decarboxylase catalyzed reactions ultimately involves the analysis of the configuration of a methylene group bearing two different isotopes of hydrogen. This has been accomplished by many methods [Floss & Vederas, 1982;Akhtar et al, 1984;Palcic & Floss (1985) and references cited therein], most of which involve correlation of the decarboxylation product with a material of known stereochemistry by a series of enzymatic or chemical reactions. NMR methods have also been employed; both direct NMR (Nakazawa et al, 1981) and NMR of camphanamide derivatives of the product amines with europium shift reagents (Santaniello et al, 1979;Orr & Gould, 1982;Orr et al, 1984) may permit configurational assignment.…”

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Stereochemistry of lysine formation by meso-diaminopimelate decarboxylase from wheat germ: use of proton-carbon-13 NMR shift correlation to detect stereospecific deuterium labeling

Kelland¹,

Palcic²,

Pickard³

et al. 1985

Biochemistry

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The stereochemical course of the wheat germ meso-diaminopimelate (DAP) decarboxylase reaction is compared to that of the decarboxylase isolated from Bacillus sphaericus, which has been reported to proceed with an unusual inversion of configuration [Asada, Y., Tanizawa, K., Sawada, S., Suzuki, T., Misono, H., & Soda, K. (1981) Biochemistry 20, 6881-6886]. Reaction of each enzyme with either unlabeled diaminopimelic acid in D2O or [2,6-2H2]diaminopimelic acid in H2O gave stereospecifically deuterium-labeled lysine samples that were derivatized with (-)-camphanoyl chloride and diazomethane. Analysis by two-dimensional 1H-13C heteronuclear NMR shift correlation spectroscopy with 2H decoupling confirmed the stereochemistry of the B. sphaericus enzyme reaction and showed that the eukaryotic wheat germ meso-DAP decarboxylase also operates with inversion of configuration. This suggests similar mechanisms for the prokaryotic and eukaryotic enzymes and contrasts the retention mode observed with other pyridoxal phosphate dependent alpha-decarboxylases.

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confidence: 98%

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confidence: 99%

Stereochemistry of lysine formation by meso-diaminopimelate decarboxylase from wheat germ: use of proton-carbon-13 NMR shift correlation to detect stereospecific deuterium labeling

Kelland¹,

Palcic²,

Pickard³

et al. 1985

Biochemistry

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“…Such compounds find continuing use in work on enzyme mechanisms (15,16,39,40). In addition, Mitsunobu cyclization and hydroxide opening of N-acyl serines stereospecifically labelled with hydrogen isotopes at C-3 permits facile interconversion of the 3R and 3S isomers.…”

Section: Discussionmentioning

confidence: 99%

“…N-Phthalimido-3-oxoalanine phenylmethyl ester (15) The literature preparation was adapted (43). A solution containing 30.0g (0.101 mol) of N-(phtha1imido)glycine phenylmethyl ester (44) in 250 mL of benzyl formate (dried over phosphorus pentoxide) was cooled to 5°C and 220mL of a THF solution of potassium tertbutoxide (I M) was added over 1 h. The mixture was kept at 5°C for 36 h and quenched at O°C by the addition of 10 mL of glacial acetic acid (178 mmol) in 250 mL of dry benzene.…”

Section: (Z)-2-acetamido-3-methoxyacrylic Acid ( 9 )mentioning

confidence: 99%

“…Since serine p-lactones are versatile intermediates for synthesis of important P-substituted alanines 3 (Scheme 1) (12), and the availability of the latter compouds stereospecifically labelled with hydrogen isotopes at C-3 would be useful for studies of enzyme mechanisms (15,16), we decided to examine the mode of formation of serine p-lactone 2 using Nbenzyloxycarbonyl serine (1) labelled with oxygen-18 and deuterium at C-3. The site of nucleophilic attack on 1 by water and hydroxide to form 3 and 4 (Scheme 1, Nu = OH) was also investigated.…”

Section: Introductionmentioning

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Mechanism of formation of serine β-lactones by Mitsunobu cyclization: synthesis and use of L-serine stereospecifically labelled with deuterium at C-3

Ramer¹,

Moore²,

Vederas³

1986

Can. J. Chem.

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. VEDERAS. Can. J. Chem. 64, 706 (1986).The ring closure of N-benzyloxycarbonyl-L-serine (1) under Mitsunobu conditions (Ph3P, dimethyl azodicarboxylate, -78°C) to give the corresponding p;lactone (2) is shown by deuterium and oxygen-18 labelling studies to proceed by hydroxy group activation, in contrast to analogous cyclizations of more hindered P-hydroxy acids, which usually occur by carboxy group activation. Samples of 1 stereospecifically labelled with deuterium at C-3 were prepared by hydrogenation of (2)-2-acetamido-3-methoxyacrylic acid (9) with deuterium, followed by selective Acylase I deacetylation of the 2 s isomer, removal of the protecting groups, and N-acylation of the resulting L-serine with benzyl chloroformate. Mitsunobu cyclizations of this 3R deuterated N-acyl serine, of the [hydroxy-'80] analog l g , and of the [ c a r b~x~- '~O ] derivative If show that lactonization occurs with inversion of configuration at C-3, loss of the hydroxy oxygen, and retention of the carboxy oxygens. Similar labelling experiments demonstrate that aqueous sodium hydroxide opens the p-lactone ring by exclusive attack at the carbonyl to regenerate 1 , whereas acidic hydrolysis proceeds primarily by attack of water at the C-3 methylene group of 2. This information allows interconversion of L-serines that are stereospecifically labelled at C-3 with hydrogen isotopes and affords access to other labelled P-substituted alanines. SHAWN E. RAMER, RICHARD N. MOORE et JOHN C. VEDERAS. Can. J. Chem. 64,706 (1986).Faisant appel a des etudes par marquage au deuterium et a l'oxygkne-18, on a dCmontrC que la cyclisation de la N-benzyloxycarbonyl L-strine (I), dans des conditions de Mitsunobu (Ph3P, azodicarboxylate de dimethyle, -7g°C), qui conduit h la formation de la p-lactone corespondante se produit par le biais d'une activation du groupement hydroxyle; ceci est en opposition avec ce qui se produit lors de cyclisations analogues d'acides P-hydroxyles plus empCchCs qui se produisent habituellement par le biais d'une activation du groupement carboxyle. On a prtpart des tchantillons de 1 marques sttr6os@cifiquement par du deuterium en C-3 en proctdant a une hydrogenation de l'acide acktamido-2 methyoxy-3 acryliques-(2) (9) avec du deuterium suivie d'une deacetylation stlective de l'isomkre 2-(S) par 1'Acylase I, de l'enlkvement des groupes protecteurs et finalement d'une N-acylation de la L-strine qui en rCsulte par du chloroformate de benzyle. Les cyclisations, selon Mitsunobu, de cette N-acyl sCrine deutkrte en 3(R), de son analogue l g portant un hydroxyle "0 et du derive lf portant un carboxyle ''0 demontrent que la lactonisation se produit avec une inversion de configuration en C-3, avec une perte d'oxygkne de l'hydroxyle et avec retention des oxygknes des groupements carboxyles. Des experiences semblables de marquage ont permis de dkmontrer que, sous l'influence de l'hydroxyde de sodium aqueux, le cycle de la p-lactone s'ouvre par une attaque qui se produit exclusivement au niveau du groupement carbonyle pour regentrer l...

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Die faszinierenden Alkaloide aus Yuzuriha

Heathcock

1992

Angewandte Chemie

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Die orientalische Pflanze Yuzuriha (Daphniphyllum macropodum) bildet eine Gruppe faszinierender polycyclischer, vom Squalen abgeleiteter Alkaloide, an denen sich der Stand der organischen Synthesechemie messen laBt. Die bezaubernden Strukturen dieser Naturstoffe haben uns dazu angeregt, zwei ziemlich verschiedene Synthesen zu entwerfen und zu untersuchen. Dieser Ubersichtsartikel stellt beide Synthesewege vor und vergleicht sie miteinander. Dem ersten Ansatz lag eine Syntheseplanung auf der Basis von Coreys Netzwerkanalyse zugrunde, bei der ein effzienter Aufbau des polycyclischen Kohlenstoffgerusts im Vordergrund steht. Wir konnten eine strategische Bindung identiftzieren und konzipierten die Synthese so, daB diese Bindung zum SchluB gekniipft wurde. Die auf dieser Grundlage entwickelte Synthese verlief glatt bis zur Abspaltung funktioneller Gruppen, die einzig zur Bildung der strategischen Bindung eingebaut worden waren. Obwohl wir diese Probleme schlieljlich losen konnten, envies sich die Synthese als zu lang, und der Aufbau eines der asymmetrischen Zentren verlief nicht stereokontrolliert. Der zweite Syntheseansatz basierte auf einem moglichen Biosyntheseweg fur eines der Alkaloide und ermoglichte einen erstaunlich leichten Zugang zu den einfacheren Vertretern dieser Verbindungsklasse. Der Erfolg dieser Synthese fuhrte zu einem konkreten Vorschlag fur die Biosynthese dieser Alkaloide und zur Entdeckung einer erstaunlichen Umsetzung, die in Schema 21 wiedergegeben ist. Bei dieser prazedenzlosen Reaktion wird ein acyclisches Squalen-Derivat durch schrittweise Umsetzung mit Allenveltschemikalien in ein pentacyclisches Alkaloid verwandelt. Dabei werden in einem Reaktionsschritt vier Kohlenstoff-Kohlenstoff-, zwei Kohlenstoff-Stickstoff-und eine Kohlenstoff-Wasserstoff-Bindung geknupft ! Isolierung und Strukturaufklarung der AlkaloideIm Orient wachst ein Baum, dem die Japaner den Namen ,,Yuzuriha" gegeben haben. Frei iibersetzt heiljt das ,,Blatter von Hand zu Hand weiterreichen". Dieser merkwurdige Name leitet sich von dem ungewohnlichen Wachstumsverhalten dieses Baumes (Daphniphyllum macropodum Miquel) ab, der in jedem Fruhling einen vollstandigen Satz neuer Blatter

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Chapter 9 Pyridoxal phosphate-dependent enzymic reactions: mechanism and stereochemistry

Cited by 8 publications

References 174 publications

Stereochemistry of lysine formation by meso-diaminopimelate decarboxylase from wheat germ: use of proton-carbon-13 NMR shift correlation to detect stereospecific deuterium labeling

Stereochemistry of lysine formation by meso-diaminopimelate decarboxylase from wheat germ: use of proton-carbon-13 NMR shift correlation to detect stereospecific deuterium labeling

Mechanism of formation of serine β-lactones by Mitsunobu cyclization: synthesis and use of L-serine stereospecifically labelled with deuterium at C-3

Die faszinierenden Alkaloide aus Yuzuriha

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