scholarly journals Nickel-Catalyzed β-Carboxylation of Ynamides with Carbon Dioxide

Synlett ◽  
2019 ◽  
Vol 30 (09) ◽  
pp. 1048-1052 ◽  
Author(s):  
Ryohei Doi ◽  
Taichi Okano ◽  
Iman Abdullah ◽  
Yoshihiro Sato

A nickel-catalyzed β-selective hydrocarboxylation of ynamides to give protected dehydro-β-amino acids was developed. The key to exclusive β-selectivity was the use of diethylzinc as a reductant in the presence of a magnesium salt. The reaction was conducted with bis(acetylacetonato)nickel(II) instead of costly and sensitive bis(1,5-cyclooctadiene)nickel(0). In addition, the optimized ligand was inexpensive 1,5-cyclooctadiene. Investigation of the substrate scope revealed that both nitrogen and alkyne substituents have marked effects on the reaction efficiency. We obtained experimental clues that indicated the formation of a vinylzinc intermediate that forms a C–C bond with CO2.

2016 ◽  
Vol 4 (3) ◽  
pp. 3170-3176 ◽  
Author(s):  
Sreedipta Chatterjee ◽  
Sadhana Rayalu ◽  
Spas D. Kolev ◽  
Reddithota J. Krupadam

1961 ◽  
Vol 39 (11) ◽  
pp. 1717-1735 ◽  
Author(s):  
P. G. Scholefield

The cumulative entry of amino acids into Ehrlich ascites carcinoma cells is due to the presence of active transport systems, each with its own specific range of substrates. Several amino acids and amino acid analogues may have an affinity for the same transport system and thus may inhibit transport of other amino acids by acting as competitive inhibitors or competitive substrates. Loss of methionine from ascites cells takes place by a diffusion process which obeys Fick's law. Leucine accumulation by ascites cells is small and is increased on addition of certain other amino acids. The increase is not due to inhibition of leucine oxidation as increase in the rate of production of radioactive carbon dioxide from labeled leucine also occurs. Kinetic aspects of these results are discussed.


2004 ◽  
Vol 76 (3) ◽  
pp. 736-741 ◽  
Author(s):  
María del Mar Caja López ◽  
Gracia P. Blanch ◽  
Marta Herraiz

1952 ◽  
Vol 30 (7) ◽  
pp. 522-528 ◽  
Author(s):  
W. B. McConnell

The carbon dioxide evolved when α-amino acids were heated for one hour at 85 °C. with ninhydrin was determined in a partially evacuated microdiffusion cell. Distillation of solvent from one chamber to the other was minimized by keeping the ionic concentrations of the reaction mixture and absorbing mixture approximately equal. The method was useful for samples of amino acids which liberated from 0.06 to 0.3 mgm. of carbon dioxide. The average deviation from the mean was somewhat less than 1% for samples liberating 0.2 mgm. of carbon dioxide. Use of the method for routine analysis of enzymatic digests resulted in substantial saving of time and material.


1963 ◽  
Vol 41 (3) ◽  
pp. 737-743 ◽  
Author(s):  
H. Reisener ◽  
A. J. Finlayson ◽  
W. B. McConnell ◽  
G. A. Ledingham

When uredospores of wheat stem rust were shaken for 3 hours with phosphate buffer (pH 6.2) containing propionate-1-C14, -2-C14, or -3-C14, about 55% of the carbon-14 was removed from the solution. With propionate-1-C14, most of the carbon-14 taken up was released as carbon dioxide-C14, whereas about 20% and 31% of propionate carbon 2 and carbon 3, respectively, was incorporated into the spores. The specific activity of a fraction consisting of the free amino acids of a hot-alcohol and hot-water extract of the spores increased markedly with increase in the position number of propionate in which the carbon-14 was located. A similar relation was observed for other fractions such as soluble carbohydrates, ether-soluble material, organic acids, and insoluble residue from spores. The most active amino acids isolated were glutamic acid, γ-aminobutyric acid, and alanine. Partial degradations showed that with propionate-2-C14 the carboxyl groups of glutamic acid were especially radioactive, whereas with propionate-3-C14 the internal carbons were most radioactive.It is concluded that propionate metabolism in the rust spores involved conversion of carbon 1 to carbon dioxide, and utilization of carbons 2 and 3 as acetate with carbon 2 behaving as the carboxyl carbon.


1990 ◽  
Vol 120 (7) ◽  
pp. 700-710 ◽  
Author(s):  
Arthur L. Black ◽  
Rajen S. Anand ◽  
Michael L. Bruss ◽  
Crawford A. Brown ◽  
James A. Nakagiri

1956 ◽  
Vol 34 (1) ◽  
pp. 511-519 ◽  
Author(s):  
G. H. N. Towers ◽  
D. C. Mortimer

Of the keto acids identified in leaves of sugar beet and other plants exposed to C14O2, pyruvic acid was found to be the only one labelled in light periods up to 45 sec. α-Ketoglutaric and glyoxylic acids became radioactive after about 45 sec. Radioactive hydroxypyruvate was not identified under these conditions and labelled oxaloacetate was detected only in trace amounts after 60 sec. in Scenedesmus. In contrast glycine and serine were labelled after 10 sec. under comparable conditions and aspartic acid was appreciably labelled after 30 sec. The effect on the radioactivity of the keto acids of an additional period intracer-free air, with and without light, as well as the dark incorporation of C14O2 was studied. These results are discussed in relation to the role of the ketoacids in photosynthesis. It is concluded that the synthesis of amino acids such as glycine, serine, and aspartic acid may be effected by mechanisms other than transamination in green leaves in the light.


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