A Simple Synthesis of 2-Methoxypyridine-3-carbonitriles

Victory, P.; Borrell, Jos I.; Vidal‐Ferran, Anton

doi:10.3987/com-92-6236

Cited by 28 publications

(7 citation statements)

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“…S37-S39), consistent with previous reactions of 17 with carbonyl compounds. 35,36 Decarboxylation at 80 °C produced the tricarballylic acid 19 (33%), which is one of the polycarboxylic acid detected in meteorites, 9 reinforcing the potential role of nitriles in prebiotic chemistry. 18 Transformation of tricarballylic acid to citric acid 14 on meteorites has been proposed.…”

mentioning

confidence: 90%

Cyanide as a Primordial Reductant enables a Protometabolic Reductive Glyoxylate Pathway

Krishnamurthy

Yadav

Pulletikurti

et al. 2021

Preprint

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Investigation of prebiotic chemical pathways leading to protometabolic forerunners of metabolism has been largely based on bio-inspired (iron-mediated) reductive conversion of carbon dioxide and of carboxylic acid substrates.1,2 While attractive from a parsimony point of view, this approach has been challenging with debatable outcomes.3,4 Herein, we show that cyanide reacts with citric acid cycle (TCA) intermediates and derivatives and acts as a primordial reducing agent mediating abiotic reductive transformations. The hydrolysis of the cyanide adducts followed by decarboxylation enables the efficient reductive-decarboxylative transformation of oxaloacetate to malate and fumarate to succinate while pyruvate and α-ketoglutarate are not reduced. In the presence of glyoxylate,5,6 malonate7 and malononitrile,8 alternative pathways emerge, which after decarboxylation produce metabolic intermediates and related compounds also found in meteorites.9 These results, along with the previous demonstration of the metal-free alpha-keto analog of the reverse-TCA cycle,4,6 suggest that (a) alternative paradigms of cyanide-based protometabolic reactions bypassing the abiotic reductive-carboxylation steps can be prebiotically viable, (b) a novel reductive glyoxylate pathway can be a precursor to the r-TCA cycle and (c) the type of sophisticated carboxylation and reduction chemistries which are part of extant metabolic cycles10,11 are an evolutionary invention mediated by complex metalloproteins11.

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confidence: 90%

Cyanide as a Primordial Reductant enables a Protometabolic Reductive Glyoxylate Pathway

Krishnamurthy

Yadav

Pulletikurti

et al. 2021

Preprint

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“…The intermediates 234 ± 236 cyclise in acid or basic media to give 3,4-dihydro-1,6-naphthyridin-2(1H )-ones 237 ± 239 (Scheme 4). 208,209 Cyclisation of piperidone 240 yields 1,6-naphthyridine monohydrate 241. An X-ray diffraction study showed that the C(2)7N(1) bond (1.362 # A) is longer than these bonds in other cyclic amides due to less efficient conjugation with the carbonyl group.…”

Section: Synthesis Of Naphthyridines Fused To a Thiophene Ringmentioning

confidence: 99%

Naphthyridines. Structure, physicochemical properties and general methods of synthesis

Литвинов¹,

Roman²,

Dyachenko³

2000

Russ. Chem. Rev.

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“…Another example of the importance of protonation in the chemistry of nitriles is the intramolecular cyclization of α,ω-dinitrile compounds in the presence of hydrogen halides. This reaction is very useful for the synthesis of substituted piridopyrimidines and naftyridines, among other nitrogenated heterocycles, , yielding a new substituted pyridine (Z = C−R) or pyrimidine (Z = N) ring (see Scheme ). The results obtained for a wide range of 1,5-dinitrile intramolecular cyclizations led us to postulate a reaction mechanism,6a in which the position of the halogen atom in the final product is determined by the relative basicities of the nitrile groups.…”

Section: Introductionmentioning

confidence: 99%

“…Analysis of the available experimental data ,, in light of the proposed mechanism provided valuable information about the relative basicity of nitriles and, so, allowed the derivation of a few empirical rules . However, both the uncertainties arising from its indirect origin and the limited number of those empirical rules made their use difficult as predictive tools in nitrile chemistry.…”

Section: Introductionmentioning

confidence: 99%

A Priori Prediction of Substituent and Solvent Effects in the Basicity of Nitriles

et al. 1998

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The relative basicity of a series of nitriles in the gas phase, chloroform, and aqueous solution is studied using ab initio and state of the art SCRF methods. Theoretical results reproduce well the available experimental data for a large series of nitrile derivatives. The origin of basicity differences in solution within the series is analyzed. The impact of the results in the understanding of nitrile chemistry is discussed.

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A Simple Synthesis of 2-Methoxypyridine-3-carbonitriles

Cited by 28 publications

References 0 publications

Cyanide as a Primordial Reductant enables a Protometabolic Reductive Glyoxylate Pathway

Cyanide as a Primordial Reductant enables a Protometabolic Reductive Glyoxylate Pathway

Naphthyridines. Structure, physicochemical properties and general methods of synthesis

A Priori Prediction of Substituent and Solvent Effects in the Basicity of Nitriles

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