Oxidative reactions of the pentose pathway and the origin of reducing equivalents for the biosynthesis of rubber inHevea brasiliensis latex

Author(s):  
Barbar�n Arregu�n ◽  
Roberto Arregu�n-Espinosa
Author(s):  
Jack Rowbotham ◽  
Oliver Lenz ◽  
Holly Reeve ◽  
Kylie Vincent

<p></p><p>Chemicals labelled with the heavy hydrogen isotope deuterium (<sup>2</sup>H) have long been used in chemical and biochemical mechanistic studies, spectroscopy, and as analytical tracers. More recently, demonstration of selectively deuterated drug candidates that exhibit advantageous pharmacological traits has spurred innovations in metal-catalysed <sup>2</sup>H insertion at targeted sites, but asymmetric deuteration remains a key challenge. Here we demonstrate an easy-to-implement biocatalytic deuteration strategy, achieving high chemo-, enantio- and isotopic selectivity, requiring only <sup>2</sup>H<sub>2</sub>O (D<sub>2</sub>O) and unlabelled dihydrogen under ambient conditions. The vast library of enzymes established for NADH-dependent C=O, C=C, and C=N bond reductions have yet to appear in the toolbox of commonly employed <sup>2</sup>H-labelling techniques due to requirements for suitable deuterated reducing equivalents. By facilitating transfer of deuterium atoms from <sup>2</sup>H<sub>2</sub>O solvent to NAD<sup>+</sup>, with H<sub>2</sub> gas as a clean reductant, we open up biocatalysis for asymmetric reductive deuteration as part of a synthetic pathway or in late stage functionalisation. We demonstrate enantioselective deuteration via ketone and alkene reductions and reductive amination, as well as exquisite chemo-control for deuteration of compounds with multiple unsaturated sites.</p><p></p>


Author(s):  
Luis A. Segura-Quezada ◽  
Karina R. Torres-Carbajal ◽  
Yuvraj Satkar ◽  
Kevin A. Juárez Ornelas ◽  
Narendra Mali ◽  
...  

: Iodine(III)-based reagents has been broadly used in oxidative reactions for the structural functionalization with several functional groups. Among the more relevant and useful synthetic transformations using these hypervalent γ 3 -reagents, it can be found the fluorination, chlorination, bromination as well as the iodination protocols. Herein, we present some of the most representatives oxidative halogenation procedures of arenes, olefins and alkynes dating from the oldest to the more recent advances in the area, highlighting the discovery and application of new iodine(III)-based halogenating species.


ChemInform ◽  
2013 ◽  
Vol 44 (39) ◽  
pp. no-no
Author(s):  
Erlei Zhang ◽  
Haiwen Tian ◽  
Sendong Xu ◽  
Xiaochun Yu ◽  
Qing Xu

1973 ◽  
Vol 158 (2) ◽  
pp. 763-781 ◽  
Author(s):  
Arthur I. Cederbaum ◽  
Charles S. Lieber ◽  
Diana S. Beattie ◽  
Emanuel Rubin
Keyword(s):  

1925 ◽  
Vol 9 (2) ◽  
pp. 269-284 ◽  
Author(s):  
Otto Glaser

1. For the heart rate in Pterotrachea coronata, intermediate temperatures disclose a thermal increment of 11,200 ±. This value is identical with the one reported by Crozier and Stier for the lamelli-branch, Anodonta. In the pteropod, Tiedemannia neapolitana the same temperatures typically reveal in the heart rate a µ value of 16,200 ± This agrees quantitatively with 16,300 found by Crozier and Stier for the heart of the slug, Limax maximus. 2. At high temperatures the average value of µ for Pterotrachea is 7,300: for Tiedemannia, 7,400. The corresponding averages at the lower limits are 22,000 and 23,000. 3. The great variability found near the edges of the temperature field are explicable in two ways. During intermissions characteristic of high temperatures and occurring also at low, we can assume a restorative process; while at both the upper and lower limits we may, in addition, find that reactions assume control which under ordinary circumstances never do so. Special evidence indicates that the highest temperatures employed, 27°C., and the lowest, 4°C., caused no irreversible changes in mechanism. 4. The theoretical analysis of the experimental facts makes use of Meyerhof's conception of carbohydrate metabolism and projects the cyclical nature of rhythm into the substrate of control. Assuming as a source of energy an original supply of material O, the value of 22,000 ± is assigned provisionally to a mobilization hydrolysis while 11,200 ± and 16,000 ± are attached to oxidative reactions influenced respectively by OH' and possibly Fe, or some other catalyst. The lowest value, 7,300 ± is assumed to indicate a synthetic process (lactic acid → glycogen?), possibly limited by CO2 excretion. In the present state of our knowledge, this distribution and interpretation seems to account reasonably for the experimental facts, but until we know more about the neurogenic controls, is entitled to rank only as an hypothesis.


2014 ◽  
Vol 43 (48) ◽  
pp. 17885-17888 ◽  
Author(s):  
Ellen M. Matson ◽  
John J. Kiernicki ◽  
Nickolas H. Anderson ◽  
Phillip E. Fanwick ◽  
Suzanne C. Bart

The first uranium(iii) charge separated ketyl radical complex, Tp*2U(OC·Ph2), has been isolated and acts as a potent two-electron reductant with reducing equivalents derived from both uranium and the redox-active benzophenone.


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