Potential Inhibitors of Phosphoenolpyruvate (PEP) Carboxylase: Phosphonic Acid Substrate-Analogs Derived From Stobbe-Type Condensations of Ethyl 3-(Diethoxyphosphinoyl)propanoate

1987 ◽  
Vol 40 (10) ◽  
pp. 1619 ◽  
Author(s):  
HG Mcfadden ◽  
RLN Harris ◽  
CLD Jenkins
Keyword(s):  
Phosphonic Acid ◽  
Acid Group ◽  
Pep Carboxylase ◽  
Substrate Analogs ◽  
Alkyl Groups ◽  
Potential Inhibitors ◽  
Mild Hydrolysis ◽  
Hydrolysis Of ◽  
Acid Substrate ◽  
Partial Esters

Phosphonic acid analogues of 2-(dihydroxyphosphinoy1oxy)propenoic acid (PEP), the substrate of PEP carboxylase, were prepared and tested as inhibitors of the enzyme. The required triacids were obtained by mild hydrolysis of the partial esters prepared by Stobbe-like condensation of aryl and alkyl carbonyl compounds with ethyl 3-(diethoxyphosphinoyl)propanoate. Condensations with aldehydes gave predominantly (9-propenoates while reactions with ketones gave mixtures of (E)- and (Z)-isomers and also, in some cases, products with the double bond rearranged to the &position. Although compounds tested were inhibitory, none was as effective as previously reported phosphate PEP analogues. Results indicate that the presence of a methyl group cis to the carboxylic acid group enhances inhibitory activity but that trans alkyl groups decrease inhibitor effectiveness.

Potential Inhibitors of Phosphoenolpyruvate Carboxylase. II. Phosphonic Acid Substrate Analogs Derived From Reaction of Trialkyl Phosphites With Halomethacrylates

1989 ◽  
Vol 42 (2) ◽  
pp. 301 ◽  
Author(s):  
HG Mcfadden ◽  
RLN Harris ◽  
CLD Jenkins
Keyword(s):  
Double Bond ◽  
Nucleophilic Substitution ◽  
Phosphonic Acid ◽  
Phosphoenolpyruvate Carboxylase ◽  
Reaction Conditions ◽  
Pep Carboxylase ◽  
Substrate Analogs ◽  
Trialkyl Phosphites ◽  
Potential Inhibitors ◽  
Acid Substrate

Analogues of phosphoenolpyruvate (PEP), the substrate of PEP carboxylase , were synthesized as potential inhibitors of the enzyme. Esterified analogue precursors were obtained by nucleophilic substitution of various halomethacrylate derivatives with trialkyl phosphites. Substitution of the halomethacrylates can occur either α to the leaving halogen or in the γ position with subsequent allylic shift of the double bond. The course of the reaction was influenced both by reaction conditions and the nature of the substituents on the reactants. The phosphonomethacrylates obtained were hydrolysed to PEP analogues that were found to be moderate to good inhibitors of PEP carboxylase. Phosphonomethacrylic acid derivatives bearing two halogen substituents in the γ position were found to be the most potent inhibitors of this enzyme.

scholarly journals Substrate Specificity of Atrazine Chlorohydrolase and Atrazine-Catabolizing Bacteria

2000 ◽  
Vol 66 (10) ◽  
pp. 4247-4252 ◽  
Author(s):  
Jennifer L. Seffernick ◽  
Gilbert Johnson ◽  
Michael J. Sadowsky ◽  
Lawrence P. Wackett
Keyword(s):  
Substrate Specificity ◽  
Homologous Gene ◽  
Clavibacter Michiganensis ◽  
Amino Groups ◽  
Substrate Analogs ◽  
Cell Extracts ◽  
Alkyl Groups ◽  
Chlorine Substituent ◽  
Cyano Groups ◽  
Hydrolysis Of

ABSTRACT Bacterial atrazine catabolism is initiated by the enzyme atrazine chlorohydrolase (AtzA) in Pseudomonas sp. strain ADP. Other triazine herbicides are metabolized by bacteria, but the enzymological basis of this is unclear. Here we begin to address this by investigating the catalytic activity of AtzA by using substrate analogs. Purified AtzA from Pseudomonas sp. strain ADP catalyzed the hydrolysis of an atrazine analog that was substituted at the chlorine substituent by fluorine. AtzA did not catalyze the hydrolysis of atrazine analogs containing the pseudohalide azido, methoxy, and cyano groups or thiomethyl and amino groups. Atrazine analogs with a chlorine substituent at carbon 2 and N-alkyl groups, ranging in size from methyl to t-butyl, all underwent dechlorination by AtzA. AtzA catalyzed hydrolytic dechlorination when one nitrogen substituent was alkylated and the other was a free amino group. However, when both amino groups were unalkylated, no reaction occurred. Cell extracts were prepared from five strains capable of atrazine dechlorination and known to containatzA or closely homologous gene sequences:Pseudomonas sp. strain ADP, Rhizobium strain PATR, Alcaligenes strain SG1, Agrobacterium radiobacter J14a, and Ralstonia picketti D. All showed identical substrate specificity to purified AtzA fromPseudomonas sp. strain ADP. Cell extracts fromClavibacter michiganensis ATZ1, which also contains a gene homologous to atzA, were able to transform atrazine analogs containing pseudohalide and thiomethyl groups, in addition to the substrates used by AtzA from Pseudomonas sp. strain ADP. This suggests that either (i) another enzyme(s) is present which confers the broader substrate range or (ii) the AtzA itself has a broader substrate range.

Synthesis and Tautomerism of Curcumin Derivatives and Related Compounds

2015 ◽  
Vol 68 (2) ◽  
pp. 224 ◽  
Author(s):  
Hiroyasu Taguchi ◽  
Daijiro Yanagisawa ◽  
Shigehiro Morikawa ◽  
Koichi Hirao ◽  
Nobuaki Shirai ◽  
...  
Keyword(s):  
Parent Compound ◽  
Amyloid Plaques ◽  
Enol Form ◽  
19F Nmr ◽  
Enolic Form ◽  
Curcumin Derivatives ◽  
Alkyl Groups ◽  
Alzheimer Brain ◽  
Hydrolysis Of ◽  
Related Compounds

1,7-Bis(4′-hydroxy-3′-trifluoromethoxyphenyl)-1,6-heptadiene-3,5-dione (2a), related to curcumin, and thirteen 4-substituted derivatives were prepared and their keto/enol ratio in DMSO[D6] was determined by 19F NMR because the enolic form of these related curcumins had been shown to bind to amyloid plaques in the Alzheimer brain. The parent compound and the 4-ethoxycarbonyl derivative were almost 100 % in the enolic form that contains a conjugated hepta-1,4,6-trien-3-on-5-ol backbone. Enolisation decreased to varying amounts in the derivatives that had 4-substituted alkyl groups. Attempts to prepare the 4-hydroxypropyl derivative by hydrolysis of O-methoxymethyl 2m or O-tetrahydropyranyloxy 2n protected derivatives led to cyclised products. A related pyrimidine compound 6b that mimicked a fixed enol form was also prepared.

ChemInform Abstract: Modern Advances of Chemical Methods for the Introduction of a Phosphonic Acid Group

ChemInform ◽  
2012 ◽  
Vol 43 (9) ◽  
pp. no-no
Author(s):  
Charles S. Demmer ◽  
Niels Krogsgaard-Larsen ◽  
Lennart Bunch
Keyword(s):  
Phosphonic Acid ◽  
Acid Group ◽  
Chemical Methods ◽  
Phosphonic Acid Group

scholarly journals Solar H2 evolution in water with modified diketopyrrolopyrrole dyes immobilised on molecular Co and Ni catalyst–TiO2 hybrids

2017 ◽  
Vol 8 (4) ◽  
pp. 3070-3079 ◽  
Author(s):  
Julien Warnan ◽  
Janina Willkomm ◽  
Jamues N. Ng ◽  
Robert Godin ◽  
Sebastian Prantl ◽  
...  
Keyword(s):  
Metal Oxide ◽  
Phosphonic Acid ◽  
Acid Group ◽  
Side Chain ◽  
Oxide Surfaces ◽  
Ni Catalyst ◽  
H2 Evolution ◽  
Metal Oxide Surfaces ◽  
Phosphonic Acid Group

A series of diketopyrrolopyrrole (DPP) dyes with a terminal phosphonic acid group for attachment to metal oxide surfaces were synthesised and the effect of side chain modification on their properties investigated.

A synthesis and some reactions of 7-Oxabicyclo[2.2.1]heptan-2-one

1983 ◽  
Vol 36 (12) ◽  
pp. 2473 ◽  
Author(s):  
J Moursounidis ◽  
D Wege
Keyword(s):  
Thermal Decomposition ◽  
Alder Reaction ◽  
Diels Alder ◽  
Acid Mixture ◽  
Diels Alder Reaction ◽  
Reaction Proceeds ◽  
Atom Migration ◽  
Acyl Azide ◽  
Mild Hydrolysis ◽  
Hydrolysis Of

Diels-Alder reaction between furan and α-chloroacrylonitrile gives a mixture of exo-2-chloro-and endo-2-chloro-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitrile (4) and (5). Mild hydrolysis affords the corresponding α-chloro acid mixture, from which the endo carboxylic acid may be removed through iodo lactone formation. Catalytic hydrogenation of (4) and (5) followed by hydrolysis, acyl azide formation, Curtius rearrangement, and hydrolysis of the resulting mixture of a-chloro isocyanates yields 7-oxabicyclo[2.2.l]heptan-2-one (1) in preparatively useful amounts. Reduction of (1) gives only endo alcohol, and Baeyer-Villiger reaction proceeds with exclusive bridgehead atom migration. Thermal decomposition of the sodium salt of the p-toluenesulfonylhydrazone of (1) affords 7-oxatricyclo[2.2.1 .02,6]heptane.

Mild hydrolysis of nitriles by the immobilized nitrilase from Aspergillus niger K10

2006 ◽  
Vol 39 (1-4) ◽  
pp. 55-58 ◽  
Author(s):  
Vojtěch Vejvoda ◽  
Ondřej Kaplan ◽  
Karel Bezouška ◽  
Ludmila Martínková
Keyword(s):  
Aspergillus Niger ◽  
Mild Hydrolysis ◽  
Hydrolysis Of
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