scholarly journals Reactions of biologically inspired hydride sources with B(C 6 F 5 ) 3

2017 ◽  
Vol 375 (2101) ◽  
pp. 20170009 ◽  
Author(s):  
Lewis C. Wilkins ◽  
Nicolò Santi ◽  
Louis Y. P. Luk ◽  
Rebecca L. Melen
Keyword(s):  
Carboxylic Acid ◽  
Recent Work ◽  
Lewis Acid ◽  
The Other ◽  
Disproportionation Reaction ◽  
Transfer Hydrogenation ◽  
Acid Moiety ◽  
Biologically Inspired ◽  
Strong Lewis Acid ◽  
High Yields

The combination of 1-benzyl-1,4-dihydropyridines with the strong Lewis acid, B(C 6 F 5 ) 3 , generates a stable pyridinium borohydride species in high yields (94%) in as little as 10 min. This use of biologically inspired hydride sources further builds on the recent work of new hydride donors in the formation of borohydrides. When functionalizing the dihydropyridine with an amide or carboxylic acid moiety, a disproportionation reaction composed of a series of protonation/reduction steps is observed upon the addition of B(C 6 F 5 ) 3 . As a result, one equivalent of dihydropyridine undergoes net hydrogenation, whereas the other is dehydrogenated yielding the pyridinium counterpart in a transfer hydrogenation-type mechanism. This article is part of the themed issue ‘Frustrated Lewis pair chemistry’.

Lewis acid-mediated intramolecular addition of silyl enol ethers to internal unactivated alkynes

2001 ◽  
Vol 79 (11) ◽  
pp. 1624-1631 ◽  
Author(s):  
Ken-ichiro Imamura ◽  
Eiji Yoshikawa ◽  
Vladimir Gevorgyan ◽  
Tomoko Sudo ◽  
Naoki Asao ◽  
...  
Keyword(s):  
Lewis Acid ◽  
The Other ◽  
Enol Ethers ◽  
Unsaturated Ketones ◽  
Silyl Enol Ethers ◽  
Other Hand ◽  
High Yields

The EtAlCl2-mediated intramolecular addition of silyl enol ethers to both terminal and internal unactivated alkynes, bearing alkyl and phenyl susbstituents at the alkyne moiety, gave mono- and bicyclic β,γ-unsaturated ketones in good to excellent yields. On the other hand, the silyloxy-substituted cyclic vinylsilanes were obtained in moderate to high yields when the reactions were catalyzed by B(C6F5)3 in the presence of triethylsilane. All the reactions proceeded via endo-fashion exclusively. The mechanisms of these regiospecific Lewis acid-assisted carbocyclizations are proposed.Key words: Lewis acid, silyl enol ethers, carbocyclization, alkynes.

Stereospecific, Palladium-catalyzed C(sp3)–H Alkenylation and Alkynylation of a Proline Derivative Enabled by 8-Aminoquinoline as a Directing Group

2020 ◽  
Author(s):  
Aleksandra Balliu ◽  
Aaltje Roelofje Femmigje Strijker ◽  
Michael Oschmann ◽  
Monireh Pourghasemi Lati ◽  
Oscar Verho
Keyword(s):  
Carboxylic Acid ◽  
Building Blocks ◽  
Wide Range ◽  
Palladium Catalyzed ◽  
Directing Group ◽  
High Yields ◽  
Vinyl Iodides ◽  
Initial Results

<p>In this preprint, we present our initial results concerning a stereospecific Pd-catalyzed protocol for the C3 alkenylation and alkynylation of a proline derivative carrying the well utilized 8‑aminoquinoline directing group. Efficient C–H alkenylation was achieved with a wide range of vinyl iodides bearing different aliphatic, aromatic and heteroaromatic substituents, to furnish the corresponding C3 alkenylated products in good to high yields. In addition, we were able show that this protocol can also be used to install an alkynyl group into the pyrrolidine scaffold, when a TIPS-protected alkynyl bromide was used as the reaction partner. Furthermore, two different methods for the removal of the 8-aminoquinoline auxiliary are reported, which can enable access to both <i>cis</i>- and <i>trans</i>-configured carboxylic acid building blocks from the C–H alkenylation products.</p>

Synthesis of 3-(Cyclohexylamino)-2-arylimidazo[1,2-a]pyridine-8- carboxylic Acids Via an Efficient Three-component Condensation Reaction between Cyclohexylisocyanide and 2-Aminopyridine-3-carboxylic Acid in the Presence of Aromatic Aldehyde

2018 ◽  
Vol 21 (4) ◽  
pp. 298-301 ◽  
Author(s):  
Ghasem Marandi
Keyword(s):  
Biological Sciences ◽  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
High Performance ◽  
Condensation Reaction ◽  
Aromatic Aldehydes ◽  
New Materials ◽  
One Pot ◽  
High Yields ◽  
Benzaldehyde Derivatives

Aim and Objective: The reaction of cyclohexylisocyanide and 2-aminopyridine-3- carboxylic acid in the presence of benzaldehyde derivatives in ethanol led to 3-(cyclohexylamino)-2- arylimidazo[1,2-a]pyridine-8-carboxylic acids in high yields. In a three component condensation reaction, isocyanide reacts with 2-aminopyridine-3-carboxylic acid and aromatic aldehydes without any prior activation. Material and Methods: The synthesized products have stable structures which have been characterized by IR, 1H, 13C and Mass spectroscopy as well as CHN-O analysis. Results: In continuation of our attempts to develop simple one-pot routes for the synthesis of 3- (cyclohexylamino)-2-arylimidazo[1,2-a]pyridine-8-carboxylic acids, aromatic aldehydes with divers substituted show a high performance. Conclusion: In conclusion, this study introduces the art of combinatorial chemistry using a simple one-pot procedure for the synthesis of new materials which are interesting compounds in medicinal and biological sciences.

Extending Epistemic Virtue

2018 ◽  
Author(s):  
Heather Battaly
Keyword(s):  
Recent Work ◽  
Virtue Epistemology ◽  
Extended Cognition ◽  
The Other ◽  
Epistemic Virtue ◽  
Virtue Responsibilism

What would happen if extended cognition (EC) and virtue-responsibilism (VR) were to meet? Are they compatible, or incompatible? Do they have projects in common? Would they, as it were, end their meeting early, or stick around but run out of things to say? Or, would they hit it off? This chapter suggests that VR and EC are not obviously incompatible, and that each might fruitfully contribute to the other. Although there has been an explosion of recent work at the intersection of virtue epistemology and EC, this work has focused almost exclusively on the reliabilist side of virtue epistemology. Little has been said about the intersection of VR and EC. This chapter takes initial steps toward filling that gap.

Hydroxyl-containing bis(sulfonates). Reaction of 1,4-dibromo-2,3-butanedione with water, methanol and sodium sulfite

2021 ◽  
pp. 1-12
Author(s):  
Gerasimos M. Tsivgoulis ◽  
Dimitris G. Vachliotis ◽  
Golfo G. Kordopati ◽  
Panayiotis V. Ioannou
Keyword(s):  
13C Nmr ◽  
Sodium Sulfite ◽  
The Other ◽  
Carbonyl Carbon ◽  
1H And 13C Nmr ◽  
Sodium Sulfonate ◽  
Pure Product ◽  
Methylene Groups ◽  
New Type ◽  
High Yields

Sulfonates are well-known substances with a variety of applications, e.g. as surfactants. On the other hand, bis(sulfonates) bearing hydroxyl or keto group(s) in between the sulfonate groups can be used with or without further modification as starting materials for the preparation of new type of molecules capable to form either complexes or in general supramolecular structures. The synthesis of three hydroxyl-bearing bis(sulfonates), 2-hydroxypropane-1,3-bis(sodium sulfonate) 4, DL-2,3-dihydroxybutane-1,4-bis(sodium sulfonate) 8, and sodium 2,3,4-trihydroxy-1-sulfonate 7 (as by-product) via the Strecker sulfonation are described. Interestingly, under similar conditions, sulfonation of 1,4-dibromo-2,3-butanedione 9 was found to be very complicated and no pure product could be isolated, despite previously reported results on sulfonation of α-halogenated ketones in high yields. There are indications that SO3 2 -  attacks at the carbonyl carbon of 9 followed by rearrangement and expulsion of SO4 2 - . 1,4-dibromo-2,3-butanedione 9, bearing two keto groups next to methylene groups, can potentially exist as enols or in the case of its solution in hydroxylic solvents in the form of hemiketals or geminal diols. This behavior of 9 when is dissolved in CDCl3, CD3OD and D2O was studied by means of UV-Vis, 1H and 13C NMR and the nature of the adducts formed was elucidated.

scholarly journals Purification, properties and comparative specificities of the enzyme prolyl-transfer ribonucleic acid synthetase from Phaseolus aureus and Polygonatum multiflorum

1965 ◽  
Vol 97 (1) ◽  
pp. 112-124 ◽  
Author(s):  
PJ Peterson ◽  
L Fowden
Keyword(s):  
Carboxylic Acid ◽  
Enzyme Preparation ◽  
Enzymic Activity ◽  
The Other ◽  
Asparagus Officinalis ◽  
Acid Activation ◽  
Phaseolus Aureus ◽  
Substrate Specificities ◽  
Imino Acids ◽  
Ammonium Sulphate Fractionation

1. A prolyl-s-RNA synthetase (prolyl-transfer RNA synthetase) has been purified about 250-fold from seed of Phaseolus aureus (mung bean), a species not producing azetidine-2-carboxylic acid, and more than 10-fold from rhizome apices of Polygonatum multiflorum, a liliaceous species containing azetidine-2-carboxylic acid. The latter enzyme was unstable during ammonium sulphate fractionation. 2. The enzymes exhibited different substrate specificities towards the analogue. That from Phaseolus, when assayed by the ATP-PP(i) exchange, showed azetidine-2-carboxylic acid activation at about one-third the rate with proline. Both labelled imino acids gave rise to a labelled aminoacyl-s-RNA. The enzyme from Polygonatum, however, activated only proline. 3. The enzyme from Polygonatum also formed a labelled prolyl-s-RNA with Phaseolus s-RNA but at a lower rate than when the Phaseolus enzyme was used. No reaction occurred when the Phaseolus enzyme was coupled with Polygonatum s-RNA, and only a very slight one was observed when both enzyme and s-RNA came from Polygonatum. 4. Protein preparations from seeds of Pisum sativum, another species not producing azetidine-2-carboxylic acid, also activated the analogue in addition to proline, whereas those from rhizome and seeds of Convallaria, the species from which the analogue was originally isolated, failed to activate it. However, a liliaceous species not producing the analogue, Asparagus officinalis, activated it. 5. Of the other proline analogues investigated, only 3,4-dehydro-dl-proline and l-thiazolidine-4-carboxylic acid were active with the enzyme preparation from Phaseolus. 6. pH optima of 7.9 and 8.4 were established for the enzymes from Phaseolus and Polygonatum respectively. 7. The Phaseolus enzyme was specific for ATP and PP(i). Mn(2+) partially replaced the requirement for Mg(2+) as cofactor. Preincubation with p-chloromercuribenzoate at a concentration of 0.5mm or higher produced over 99% inhibition of the Phaseolus enzyme. One-half the enzymic activity was destroyed by preheating for 5min. at 62 degrees in tris-hydrochloric acid buffer, pH7.9. 8. All experimental evidence supports the hypothesis that azetidine-2-carboxylic acid and proline are activated by the same enzyme in Phaseolus preparations, whereas the analogue was inactive in all Polygonatum preparations. The possible nature of this different substrate behaviour is discussed.

New insights about the host–guest chemistry of the tungsten oxo complex of calix[4]arene, and novel "one pot" difunctionalizations of calix[4]arene using tetrachlorometal(VI) oxide (M = Mo, W)

2004 ◽  
Vol 82 (10) ◽  
pp. 1452-1461 ◽  
Author(s):  
Pascal Mongrain ◽  
Jasmin Douville ◽  
Jonathan Gagnon ◽  
Marc Drouin ◽  
Andreas Decken ◽  
...  
Keyword(s):  
Water Molecule ◽  
Lewis Acid ◽  
Chemical Shifts ◽  
Strong Interactions ◽  
Ir Absorption ◽  
One Pot ◽  
X Ray ◽  
Strong Lewis Acid ◽  
Successful Removal ◽  
Coordinated Water

The strong Lewis acid tungsten oxo complex of calix[4]arene can be obtained in both hydrated and non-hydrated forms. This complex coordinates a water molecule inside the cavity via strong O···W interactions with relatively short distances of 2.284(4) and 2.329(2) Å for the tungsten oxo complex of calix[4]arene··H2O·aniline (1), and the tungsten oxo complex of calix[4]arene·H2O·toluene (2·toluene), respectively. The strong interactions are also deduced by the relatively high H2O elimination temperature observed by TGA and DSC (above 200 °C). The coordinated water molecule inside the calix[4]arene cavity is characterized by a strong IR absorption at 3616 cm–1, and a narrow resonance at ~1.2 ppm (the chemical shifts of the uncoordinated water are 1.55 and 1.60 ppm in C6D6 and CDCl3, respectively). This water molecule gives rise to H-bonds with aniline in 1. The tungsten oxo complex of 5,11,17,23-tetrabromocalix[4]arene (4), also binds H2O as the characteristic signatures are observed. The successful removal of H2O in 2, is performed under mild conditions using bis(tetrahydrofuran)-uranyl nitrate as a competitive Lewis acid. When this reaction is performed in acetonitrile, butyronitrile or tert-butylnitrile, the corresponding tungsten oxo complexes of calix[4]arene·acetonitrile (3), ·butyronitrile (5), and ·tert-butylnitrile (6) are obtained. The use of uranyl as a H2O abstractor is unprecedented. The X-ray structure of 3 consists of a tungsten oxo complex of calix[4]arene coordinated by an acetonitrile molecule (d(W···N = 2.412(2) Å). The tetra-5,11,17,23-choromethyl-25,26,27,28-tetrahydroxycalix[4]arene reacts with M(O)Cl4 (M = Mo, W) in a 1:1 stoichiometry, via a tetra Friedel–Crafts addition of benzene or toluene, followed by a lower-rim complexation of the metal oxide, to form "flower-shaped" calix[4]arenes. This "one pot" double functionalization is unprecedented.Key words: calix[4]arene, tungsten, molybdenum, X-ray, host–guest, Friedel–Crafts, Lewis acid, uranyl, DSC, TGA.

scholarly journals Synthesis of spiro[dihydropyridine-oxindoles] via three-component reaction of arylamine, isatin and cyclopentane-1,3-dione

2013 ◽  
Vol 9 ◽  
pp. 8-14 ◽  
Author(s):  
Yan Sun ◽  
Jing Sun ◽  
Chao-Guo Yan
Keyword(s):  
Acetic Acid ◽  
Reaction Mechanism ◽  
Room Temperature ◽  
The Other ◽  
Other Hand ◽  
Three Component Reaction ◽  
High Yields

A fast and convenient protocol for the synthesis of novel spiro[dihydropyridine-oxindole] derivatives in satisfactory yields was developed by the three-component reactions of arylamine, isatin and cyclopentane-1,3-dione in acetic acid at room temperature. On the other hand the condensation of isatin with two equivalents of cyclopentane-1,3-dione gave 3,3-bis(2-hydroxy-5-oxo-cyclopent-1-enyl)oxindole in high yields. The reaction mechanism and substrate scope of this novel reaction is briefly discussed.

Part 2. The deeper structure of the Atlantic - Geological hypotheses and the earth's crust under the oceans

1954 ◽  
Vol 222 (1150) ◽  
pp. 341-348 ◽  
Keyword(s):  
Heat Flow ◽  
Recent Work ◽  
Sea Water ◽  
Volcanic Rocks ◽  
The Other ◽  
Ocean Floor ◽  
Peridotite Xenoliths ◽  
The Earth ◽  
Southern Rhodesia ◽  
Mohorovičić Discontinuity

Recent work has determined the depth of the Mohorovičić discontinuity at sea and has made it likely that peridotite xenoliths in basaltic volcanic rocks are samples of material from below the discontinuity. It is now possible to produce a hypothetical section showing the transition from a continent to an ocean. This section is consistent with both the seismic and gravity results. The possible reactions of the crust to changes in the total volume of sea water are dis­cussed. It seems possible that the oceans were shallower and the crust thinner in the Archean than they are now. If this were so, some features of the oldest rocks of Canada and Southern Rhodesia could be explained. Three processes are described that might lead to the formation of oceanic ridges; one of these involves tension, one compression and the other quiet tectonic conditions. It is likely that not all ridges are formed in the same way. It is possible that serpentization of olivine by water rising from the interior of the earth plays an important part in producing changes of level in the ocean floor and anomalies in heat flow. Finally, a method of reducing gravity observations at sea is discussed.

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