3228-27-1Relevant articles and documents
A simple, rapid method for the preparation of [11C]formaldehyde
Hooker, Jacob M.,Schoenberger, Matthias,Schieferstein, Hanno,Fowler, Joanna S.
, p. 5989 - 5992 (2008)
A PET project: A powerful reagent for the synthesis of positron-emitting imaging molecules - [11C]formaldehyde - is accessible from [ 11C]methyl iodide and trimethylamine N-oxide (TMAO) in high yields and under mild conditions. Easy access to [11C]formaldehyde expands the scope of the carbon-11 toolbox and will lead to new reaction methodology and imaging compounds. (Chemical Equation Presented).
Enantioselective Reductive Oligomerization of Carbon Dioxide into l-Erythrulose via a Chemoenzymatic Catalysis
Bontemps, Sébastien,Clapés, Pere,Desmons, Sarah,Dumon, Claire,Fauré, Régis,Grayson-Steel, Katie,Hurtado, John,Nu?ez-Dallos, Nelson,Vendier, Laure
supporting information, p. 16274 - 16283 (2021/10/12)
A cell-free enantioselective transformation of the carbon atom of CO2has never been reported. In the urgent context of transforming CO2into products of high value, the enantiocontrolled synthesis of chiral compounds from CO2would be highly desirable. Using an original hybrid chemoenzymatic catalytic process, we report herein the reductive oligomerization of CO2into C3(dihydroxyacetone, DHA) and C4(l-erythrulose) carbohydrates, with perfect enantioselectivity of the latter chiral product. This was achieved with the key intermediacy of formaldehyde. CO2is first reduced selectively by 4e-by an iron-catalyzed hydroboration reaction, leading to the isolation and complete characterization of a new bis(boryl)acetal compound derived from dimesitylborane. In an aqueous buffer solution at 30 °C, this compound readily releases formaldehyde, which is then involved in selective enzymatic transformations, giving rise either (i) to DHA using a formolase (FLS) catalysis or (ii) to l-erythrulose with a cascade reaction combining FLS and d-fructose-6-phosphate aldolase (FSA) A129S variant. Finally, the nature of the synthesized products is noteworthy, since carbohydrates are of high interest for the chemical and pharmaceutical industries. The present results prove that the cell-freede novosynthesis of carbohydrates from CO2as a sustainable carbon source is a possible alternative pathway in addition to the intensely studied biomass extraction andde novosyntheses from fossil resources.
Formation of Glyoxylic Acid in Interstellar Ices: A Key Entry Point for Prebiotic Chemistry
Eckhardt, André K.,Bergantini, Alexandre,Singh, Santosh K.,Schreiner, Peter R.,Kaiser, Ralf I.
supporting information, p. 5663 - 5667 (2019/03/29)
With nearly 200 molecules detected in interstellar and circumstellar environments, the identification of the biologically relevant α-keto carboxylic acid, glyoxylic acid (HCOCOOH), is still elusive. Herein, the formation of glyoxylic acid via cosmic-ray driven, non-equilibrium chemistry in polar interstellar ices of carbon monoxide (CO) and water (H2O) at 5 K via barrierless recombination of formyl (HCO) and hydroxycarbonyl radicals (HOCO) is reported. In temperature-programmed desorption experiments, the subliming neutral molecules were selectively photoionized and identified based on the ionization energy and distinct mass-to-charge ratios in combination with isotopically labeled experiments exploiting reflectron time-of-flight mass spectrometry. These studies unravel a key reaction path to glyoxylic acid, an organic molecule formed in interstellar ices before subliming in star-forming regions like SgrB2(N), thus providing a critical entry point to prebiotic organic synthesis.
Ruthenium-catalyzed reduction of carbon dioxide to formaldehyde
Bontemps, Sébastien,Vendier, Laure,Sabo-Etienne, Sylviane
supporting information, p. 4419 - 4425 (2014/04/03)
Functionalization of CO2 is a challenging goal and precedents exist for the generation of HCOOH, CO, CH3OH, and CH4 in mild conditions. In this series, CH2O, a very reactive molecule, remains an elementary C1 building block to be observed. Herein we report the direct observation of free formaldehyde from the borane reduction of CO2 catalyzed by a polyhydride ruthenium complex. Guided by mechanistic studies, we disclose the selective trapping of formaldehyde by in situ condensation with a primary amine into the corresponding imine in very mild conditions. Subsequent hydrolysis into amine and a formalin solution demonstrates for the first time that CO2 can be used as a C 1 feedstock to produce formaldehyde.
