Name: syntheses, crystallization, and spectroscopic characterization of 3,5-lutidine n-oxide dehydrate
Uploaded: 2018-04-24T14:00:00.000+00:00
Duration: 6 min 18 s
Description: Watch this Scientific Journal Video about Syntheses, Crystallization, and Spectroscopic Characterization of 3,5-Lutidine N-Oxide Dehydrate at JoVE.com

Mevcut çalışma Vicerrectoría de Investigación y Estudios de Posgrado BUAP, koleksiyonlara bilim ve Proje No tarafından desteklenen REOY-NAT14, 15, 16-G. HEAŞ-NAT17. RMG CONACyT (Meksika) burs 417887 için teşekkürler.

1. tepki
<ol><li>Bir duman mahallede bir açılan yuvarlak 100 mL şişe 0,5 mol (29.8 mL) buzul Asetik asit ile yer ve 3,5-dimethylpyridine ve H2O2 (% 35) 5 mL 0,051 mol (5.82 mL) ekleyin. Bir iç sıcaklığı 80 ° c 5 h için karışım reaksiyon sabit manyetik karıştırma altında tutun.</li>
	<li>Reaksiyon süresi sonra şişeye 24 ° c buz (yapmak değil açmak için buz Asetik asit gazları) ile serin ve aşırı Asetik asit kaldırmak için bir yüksek vakum damıtma birimine 90-120 min için takın. Dikkat: sıcak malzeme kullanmayın. Züccaciye Mağazaları yönetilebilir bir sıcaklığa ulaşıncaya kadar bekleyin. Bu aynı zamanda buharı damıtma ünitesi üst girerek önlemek olacaktır.</li>
	<li>Distile su (10 mL) iki kez herhangi bir iz Asetik asit ve karışım konsantre kaldırılması çok emin olmak için mümkün olduğunca ekleyin.</li>
</ol>2. Bazlığı ayarlama ve ayıklama
<ol><li>BI-distillated suya izole viskoz ve şeffaf ürün dağıtılması ve bir potansiyometre pH 10 saf katı Na2CO3ayarlamak için kullanın.</li>
	<li>Dikkatle çözüm 250 mL ayrılık huni içinde yer ve verimi artırmak için CHCl3 ile 5 kez 250 mL ayıklayın. Organik katmanı yeniden elde etmek ve çok katı Na2üzerinde kuru ürün içeren4 30 dk en fazla, için. Gerekirse, CHCl3istenilen miktarda sulu faz yeniden ayıklayın. Dikkat: CHCl3 uyuşukluğa ve baş dönmesine neden olabilir; özenle ve duman çuval içinde ele.</li>
	<li>Solvent düşük basınç altında yüksek vakum damıtma ünitesi ile bir çok higroskopik açık bej kristal toz (% 70) oluşumuna kadar kaldırın.</li>
</ol>3. kristalizasyon işlemi
<ol><li>4.3 g 50 ml soğuk yüksek gerçekleştirilen sıvı Kromatografi (HPLC) sınıf Dietil eter kristal toz geçiyoruz. Vakum filtre sağlam başlangıç materyali bile toz ait herhangi bir iz kaldırmak için çözüm. Filtrate bir cam Petri kabına içine dökün, gideriş o yavaş buharlaşır laboratuar buzdolabı 4 ° C'de.</li>
	<li>İki gün sonra berrak renksiz kristaller elde edilen emin olun. 310-311 K. aralığında olmalıdır erime noktası ölçmek</li>
</ol>4. analiz 3,5-Lutidine N -oksit Dehydrate
<ol><li>Prizmatik şeklinin ve renksiz, decantation şişeye'nın duvarları daha fazla x-ışını analiz üzerinden tarafından oluşmuş kristaller kaldırın. Hemen kullandıysanız, kristaller Dietil eter içinde kristal hidrasyon önlemek için tutmak.</li>
	<li>G 3,5-lutidine N -oksit kurutmak 0.4 mL NMR H1 ve yordam etkinliğini kanıtlamak için C13 analiz gerçekleştirmek için CDCl3 0.010 geçiyoruz.</li>
</ol>

<ol>
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Tüm yazarlar hiçbir çıkar çatışması beyan ederim.

Burada sunulan protokolü bir oksijen atomu 3,5-lutidine azot atomu yüzeylerde functionalization yöntemi olarak bağlamak için geleneksel bir yöntemdir. Bu teknik aynı zamanda x-ışını uygun kurutulmuş kristaller (şekil 5, Sony DSC-HX300 Cyber-atış fotoğraf makinesi ile çekilen resimler) verim de bilinmektedir. Ciddiye alıyoruz kadarıyla pek raporlar böyle kristalleri16üretim anlatmıştık. Onlar çeşitli metaller17,<sup class...

Günümüzde, dünya çapında bilim kaynakları geliştirme için düşük reaktivite ön ek reaksiyonları1,2içinbilinen aromatik grupların functionalization için yeni sentetik yollarının içine yatırım, 3. Nerede bir azot atomu bir Karbon atomu yerine koyar, pyridine, yüzük sadece karbon atomları3/ oluşan analog için benzer bir kimyasal reaktivite sunar ve genellikle bir ikame mekanizması ek yerine geçer. N-oksit varlığı arasında azot ve oksijen azot Tarih nonbonding elektron çifti oksijen atom3boş bir yörünge ile çakışma tarafından kurulan bir donör bağ ile kendine özgü. Özellikle, pyridine N-oksit vardır Lewis üsleri, çünkü onların N-O yan bir elektron verici hareket edebilir ve karşılık gelen Lewis asit-baz çifti oluşturan Lewis asidi ile birleştirebiliriz. Nucleophilicity potansiyel electrophiles doğru Lewis asitlerinin artırmak ve böylece onlara koşullar altında bir tepki nerede normal tepki değil oluşacak izin verebilirsiniz çünkü bu özellik gerekli bir kimyasal sonucu vardır. Muhtemelen böyle bileşikler en sık kullanımı nerede onlar oksidanlar4hareket çeşitli oksidasyon reaksiyonları mevcuttur. Pyridine N-oksit ve birçok yüzük functionalized türevleri biyolojik olarak aktif ve farmakolojik ajanlar5tekrarlayan molekülleri ve net kayma dağıtım farklı soğurma araçları tarafından kurulmuş olup Bazıları için6,7. Araştırmada farklı gruplar pyridine ringe iliştirmek, forma 6 - Ksilen kaynar suda isoxazolines Bankası DBU gibi katalitik bir miktar gerektirir beri bir kolay ve geleneksel yöntem üretmek için çeşitli yöntemler bilim adamları test ettik yerine-2-aminopyridine N-oksit8,9. Pyridine türevleri çeşitli onların karşılık gelen Ndönüştürülür-huzurunda katalitik bir miktar manganez oksit tetrakis(2,6-diclorophenyl) CH2Cl2/CH3 porfirin ve amonyum asetat CN8,10. Diğer pyridines CH2Cl2 H2O2 katalitik miktarları methyltrioxorhenium8,11ya da aşırı dimethyldioxirane eklenmesiyle huzurunda kullanarak onların oksitler için okside 0 ° C'de bu da neden için karşılık gelen N-oksit8,12,13,14. Bis (trimethylsilyl) peroksit varlığında trioxorhenium CH2Cl2 pyridine Nsentezi için kullanılmıştır-oksit8,11. Aminopyridine Nsentezi-oksit içeren asilasyonu Caro'nun asit (peroxomonosulfuric asit) kullanarak Ayrıca olmuştur8bildirdi. Yine de, burada bildirilen Metodolojisi ve hangi parçası Ochiai1tarafından bildirilen metodoloji kullanır daha ucuz ve erişilebilir reaktifler, H2O2 ve buzul Asetik asit kullanımı ile çok iyi sonuçlar sağlar. Üçüncül aminler hareket büyük ölçekli hazırlıklar kullanım için daha uygun bir uygulamadır, sadece % 30 hidrojen peroksit gerektirir bir tepki olarak iyi verimleri ve buzul Asetik asit 70-80 ° C arasında bir sıcaklık üretir ve arıtma işlemi kullanır Bu damıtma, katalizör ya da daha pahalı reaktifler1kullanımı olmadan gibi çoğu sentez laboratuarında mevcuttur. Belgeleri diğer yöntemlerden de sık sık zaman dilimlerini 10 / 24 h ve 100 ° C 4,8üzerindeki sıcaklıklara içerir ve X-ray analizleri için doğru biçimli kristaller verim nadiren bildirilen raporları.
Reaktif, çeşitli N -oksit türevlerinin yeterince lutidine yüzük ya Nükleofilik veya electrophilic şekilde etkinleştirmek için kullanılır. Nükleofilik veya electrophilic faktör ornatıklarla yer tarafından etkilenir. Elektron çekilmesi grupları varlık pyridine yüzükle Nükleofilik karakteristik1ana faktördür. Ücretsiz N-oksit bileşikleri Aromatik halka delocalized görevli nedeniyle x-ışını analiz için uygun kristalleri nadiren izole. Ancak, solvasyon faktör oksijen15negatif yoğunluğu stabilize etmek önemlidir.

<table><tbody><tr><td>3,5-lutidine</td><td>Sigma-Aldrich</td><td>L4206-500ML</td><td></td></tr><tr><td>Glacial acetic acid</td><td>Fermont</td><td>3015</td><td></td></tr><tr><td>Hidrogen peroxide (35%)</td><td>Sigma-Aldrich</td><td>349887-500ML</td><td></td></tr><tr><td>Na&lt;sub&gt;2&lt;/sub&gt;CO&lt;sub&gt;3&lt;/sub&gt; anhydrous</td><td>Productos Qu&amp;iacute;micos Monterrey</td><td>1792</td><td></td></tr><tr><td>Na&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; anhydrous</td><td>Alfa reactivos</td><td>25051-C</td><td></td></tr><tr><td>CHCl&lt;sub&gt;3&lt;/sub&gt;</td><td>Fermont</td><td>6205</td><td></td></tr><tr><td>Ethyl eter</td><td>Mercury Chemist</td><td>QME0309</td><td></td></tr><tr><td>Distilled water</td><td>Comercializadora Qu&amp;iacute;mica Poblana</td><td>not-existent</td><td></td></tr></tbody></table>

syntheses, crystallization, and spectroscopic characterization of 3,5-lutidine n-oxide dehydrate

3,5-lutidine N -oksit sentezi kurutmak, 1, 2-amino-pyridine-3,5-Dikarboksilik asit sentez yolu sağlandı. Ochiai ilk sigara yerine pyridines için 12 h sürecinde 1957 yılında metodolojisi kullanılmış, ama hiçbir x-ışını uygun kristalleri elde edilmiştir. Burada sunulan metodoloji kullanılan yerine halka açıkça su molekülleri ek 1' deki farklı Nükleofilik gücü confers asimetrik bir bölüm etkilemiştir. X-ışını uygun kristal bileşik 1 nereye hidrojen atomları halka içine pozitif şarj bağışlamak varlığı iki su molekülleri ile oksijen negatif yük sabitleme nedeniyle mümkün; Böyle su molekülleri de supramolecular bir etkileşim oluşturmak için hizmet vermektedir. Su molekülleri pH 10 ayarlayarak ulaşıldığında alkalin sistemi mümkündür. Önemlisi, Çift Kişilik metil halka ve tepki süresi 5 h, yerine daha çok yönlü bir yöntem yapar ve gelecekteki yüzük eklemeleri için daha geniş Kimyasal uygulamalar ile.

Protokol Ochiai'nın tekniği1, aslında bir uzantısıdır. Ancak, daha düşük sıcaklık ve daha az zaman uygulanır. Bu basit yöntem yerine konan pyridine Nolan bir çok yönlü ligand elde etmek için kullanılan-oksit modeli. 1oluşumu onaylamak için NMR 1H ve 13C analiz yordam etkinliğini test etmek için tercih edilmektedir.
Kimyasal shift <stron...

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Syntheses, Crystallization, and Spectroscopic Characterization of 3,5-Lutidine N-Oxide Dehydrate

Burada, biz sentez ve 3,5-lutidine N -oksit kristalleşme kurutmak pyridine Nklasik sentezi farklı basit bir protokol tarafından Raporu-oksit. Bu iletişim kuralı farklı başlangıç materyali kullanır ve daha az tepki zaman altında yavaş buharlaşma billurlaşır yeni bir solvated supramolecular yapısı, vermeye içerir.

İmmobilizasyonu, kristalizasyon ve spektroskopik karakterizasyonu: 3,5-Lutidine N-oksit kurutmak

The synthesis of 3,5-lutidine N-oxide dehydrate, 1, was achieved in the synthesis route of 2-amino-pyridine-3,5-dicarboxylic acid. Ochiai first used the ...

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JoVE Journal

Chemistry

Syntheses, Crystallization, and Spectroscopic Characterization of 3,5-Lutidine N-Oxide Dehydrate

8.3K Görüntüleme.  Benemérita Universidad Autónoma de Puebla. Burada, biz sentez ve 3,5-lutidine N -oksit kristalleşme kurutmak pyridine Nklasik sentezi farklı basit bir protokol tarafından Raporu-oksit. Bu iletişim kuralı farklı başlangıç materyali kullanır ve daha az tepki zaman altında yavaş buharlaşma billurlaşır yeni bir solvated supramolecular yapısı, vermeye içerir.

Video: Syntheses, Crystallization, and Spectroscopic Characterization of 3,5-Lutidine N-Oxide Dehydrate

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

Fonksiyonlu Sentezi ve Karakterizasyonu Metal-organik Altyapıları

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

Kimya

Synthesis of Indoxyl-glycosides for Detection of Glycosidase Activities

Indoxyl glycosides proved to be valuable and versatile tools for monitoring glycosidase activities. Indoxyls are released by enzymatic hydrolysis and are rapidly oxidized, for example by atmospheric oxygen, to indigo type dyes. This reaction enables fast and easy screening in vivo without isolation or purification of enzymes, as well as rapid tests on agar plates or in solution (e.g., blue-white screening, micro-wells) and is used in biochemistry, histochemistry, bacteriology and molecular biology. Unfortunately the synthesis of such substrates proved to be difficult, due to various side reactions and the low reactivity of the indoxyl hydroxyl function. Especially for glucose type structures low yields were observed. Our novel approach employs indoxylic acid ester as key intermediates. Indoxylic acid esters with varied substitution patterns were prepared on scalable pathways. Phase transfer glycosylations with those acceptors and peracetylated glycosyl halides can be performed under common conditions in high yields. Ester cleavage and subsequent mild silver mediated glycosylation yields the peracetylated indoxyl glycosides in high yields. Finally deprotection is performed according to Zempl&#233;n.

Indoxyl glycosides are well-established and widely used tools for enzyme screening and enzyme activity monitoring. Especially for glucose type structures previous syntheses proved to be challenging and low yielding. Our novel approach employs indoxylic acid esters as precious intermediates to yield a considerable number of indoxyl glycosides in good yields.

Glikosidaz Faaliyetlerinin Belirlenmesi için indoksil-glikozitler sentezi

Indoxyl glycosides proved to be valuable and versatile tools for monitoring glycosidase activities. Indoxyls are released by enzymatic hydrolysis and are ...

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the hydroxylmethylene phosphine precursor with ammonia in methanol under a nitrogen atmosphere. The N-triphosPh ligand precipitates from the solution after approximately 1 hr of reflux and can be isolated analytically pure via simple cannula filtration procedure under nitrogen. Reaction of the N-triphosPh ligand with [Ru3(CO)12] under reflux affords a deep red solution that show evolution of CO gas on ligand complexation. Orange crystals of the complex [Ru(CO)2{N(CH2PPh2)3}-&#954;3P] (2) were isolated on cooling to RT. The 31P{1H} NMR spectrum showed a characteristic single peak at lower frequency compared to the free ligand. Reaction of a toluene solution of complex 2 with oxygen resulted in the instantaneous precipitation of the carbonate complex [Ru(CO3)(CO){N(CH2PPh2)3}-&#954;3P] (3) as an air stable orange solid. Subsequent hydrogenation of 3 under 15 bar of hydrogen in a high-pressure reactor gave the dihydride complex [RuH2(CO){N(CH2PPh2)3}-&#954;3P] (4), which was fully characterized by X-ray crystallography and NMR spectroscopy. Complexes 3 and 4 are potentially useful catalyst precursors for a range of hydrogenation reactions, including biomass-derived products such as levulinic acid (LA). Complex 4 was found to cleanly react with LA in the presence of the proton source additive NH4PF6 to give [Ru(CO){N(CH2PPh2)3}-&#954;3P{CH3CO(CH2)2CO2H}-&#954;2O](PF6) (6).

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

Ruthenium phosphine complexes are widely used for homogeneous catalytic reactions such as hydrogenations. The synthesis of a series of novel tridentate ruthenium complexes bearing the N-triphos ligand N(CH2PPh2)3 is reported. Additionally, the stoichiometric reaction of a dihydride Ru&#8211;N-triphos complex with levulinic acid is described.

Rutenyum bir Serisi Sentezi, Karakterizasyonu ve Tepkime<em&gt; K</em&gt; -triphos<sup&gt; Ph</sup&gt; Kompleksi

Herein we report the synthesis of a tridentate phosphine ligand N(CH2PPh2)3 (N-triphosPh) (1) via a phosphorus based Mannich reaction of the ...

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents

Organolithium reagents are powerful tools in the synthetic chemist&#39;s toolbox. However, the extreme pyrophoric nature of the most reactive reagents warrants proper technique, thorough training, and proper personal protective equipment. To aid in the training of researchers using organolithium reagents, a thorough, step-by-step protocol for the safe and effective use of tert-butyllithium on an inert gas line or within a glovebox is described. As a model reaction, preparation of lithium tert-butyl amide by the reaction of tert-butyl amine with one equivalent of tert-butyl lithium is presented.

The safe and proper use of organolithium reagents is described.

Organolityum Reaktifleri kullanarak Güvenli litiasyon Reaksiyonlar için Protokol

Organolithium reagents are powerful tools in the synthetic chemist&#39;s toolbox. However, the extreme pyrophoric nature of the most reactive reagents ...

One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate glycosyl donor. Following azido-nitration of a glycal, the product 2-azido-1-nitrate ester can be hydrolyzed under microwave-assisted irradiation. This transformation is usually achieved using strongly nucleophilic reagents and extended reaction times. Microwave irradiation induces hydrolysis, in the absence of reagents, with short reaction times. Following denitration, the intermediate anomeric alcohol is converted, in the same pot, to the corresponding 2-azido-1-trichloroacetimidate.

A 2-azido-1-nitrate-ester can be converted to the corresponding 2-azido-1-trichloroacetimidate in a one-pot procedure. The goal of the manuscript is to demonstrate utility of the microwave reactor in carbohydrate synthesis.

One-pot mikrodalga destekli dönüşüm anomerik nitrat-esterleri Trichloroacetimidates

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate ...

Enzymatic Cascade Reactions for the Synthesis of Chiral Amino Alcohols from L-lysine

Amino alcohols are versatile compounds with a wide range of applications. For instance, they have been used as chiral scaffolds in organic synthesis. Their synthesis by conventional organic chemistry often requires tedious multi-step synthesis processes, with difficult control of the stereochemical outcome. We present a protocol to enzymatically synthetize amino alcohols starting from the readily available L-lysine in 48 h. This protocol combines two chemical reactions that are very difficult to conduct by conventional organic synthesis. In the first step, the regio- and diastereoselective oxidation of an unactivated C-H bond of the lysine side-chain is catalyzed by a dioxygenase; a second regio- and diastereoselective oxidation catalyzed by a regiodivergent dioxygenase can lead to the formation of the 1,2-diols. In the last step, the carboxylic group of the alpha amino acid is cleaved by a pyridoxal-phosphate (PLP) decarboxylase (DC). This decarboxylative step only affects the alpha carbon of the amino acid, retaining the hydroxy-substituted stereogenic center in a beta/gamma position. The resulting amino alcohols are therefore optically enriched. The protocol was successfully applied to the semipreparative-scale synthesis of four amino alcohols. Monitoring of the reactions was conducted by high performance liquid chromatography (HPLC) after derivatization by 1-fluoro-2,4-dinitrobenzene. Straightforward purification by solid-phase extraction (SPE) afforded the amino alcohols with excellent yields (93% to &#62;95%).

Chiral amino alcohols are versatile molecules for use as scaffolds in organic synthesis. Starting from L-lysine, we synthesize amino alcohols by an enzymatic cascade reaction combining diastereoselective C-H oxidation catalyzed by dioxygenase followed by cleavage of the carboxylic acid moiety of the corresponding hydroxyl amino acid by a decarboxylase.

Enzimatik Cascade reaksiyonlardan L-lizin Amino kiral alkoller sentezi için

Amino alcohols are versatile compounds with a wide range of applications. For instance, they have been used as chiral scaffolds in organic synthesis. ...

Regioselective O-Glycosylation of Nucleosides via the Temporary 2',3'-Diol Protection by a Boronic Ester for the Synthesis of Disaccharide Nucleosides

Disaccharide nucleosides, which consist of disaccharide and nucleobase moieties, have been known as a valuable group of natural products having multifarious bioactivities. Although chemical O-glycosylation is a commonly beneficial strategy to synthesize disaccharide nucleosides, the preparation of substrates such as glycosyl donors and acceptors requires&#160;tedious protecting&#160;group manipulations and a purification at each synthetic step. Meanwhile, several research groups have reported that boronic and borinic esters serve as a protecting or activating group of carbohydrate derivatives to achieve the regio- and/or stereoselective acylation, alkylation, silylation, and glycosylation. In this article, we demonstrate the procedure for the regioselective O-glycosylation of unprotected ribonucleosides utilizing boronic acid. The esterification of 2&#39;,3&#39;-diol of ribonucleosides with boronic acid makes the temporary protection of diol, and, following O-glycosylation with a glycosyl donor in the presence of p-toluenesulfenyl chloride and silver triflate, permits the regioselective reaction of the 5&#39;-hydroxyl group to afford the disaccharide nucleosides. This method could be applied to various nucleosides, such as guanosine, adenosine, cytidine, uridine, 5-metyluridine, and 5-fluorouridine. This article and the accompanying video represent&#160;useful (visual) information for the O-glycosylation of unprotected nucleosides and their analogs for the synthesis of not only disaccharide nucleosides, but also a variety of biologically relevant derivatives.

Regioselective O-Glycosylation of Nucleosides via the Temporary 2',3'-Diol Protection by a Boronic Ester for the Synthesis of Disaccharide Nucleosides

Here, we present protocols for the synthesis of disaccharide nucleosides by the regioselective O-glycosylation of ribonucleosides via a temporary protection of their 2&#39;,3&#39;-diol moieties utilizing a cyclic boronic ester. This method applies to several unprotected nucleosides such as adenosine, guanosine, cytidine, uridine, 5-methyluridine, and 5-fluorouridine to give corresponding disaccharide nucleosides.

Regioselective O- glikozilasyon nükleozitler üzerinden geçici 2', 3'-Diol koruması tarafından Boronic Ester Disaccharide nükleozitler sentezi için

Disaccharide nucleosides, which consist of disaccharide and nucleobase moieties, have been known as a valuable group of natural products having ...

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of &#945;-Imino &#947;-Lactones and Alkylidene Pyrazolones

Bispirocyclic scaffolds are one of the important structural subunits in many natural products that exhibit diverse and attractive biological activities. Recently, we have developed an efficient organocatalytic strategy, which provides facile access to a variety of enantiomerically enriched bispiro[&#947;-butyrolactone-pyrrolidin-4,4&#39;-pyrazolone] skeletons. In this paper, we demonstrate a detailed protocol for the asymmetric synthesis of drug-like bispirocyclic compounds with two spirocyclic carbon centers via an organocatyltic 1,3-dipolar cycloaddition reaction. Spirocyclization synthons &#945;-imino &#947;-lactones and alkylidene pyrazolones are prepared first, which are then subjected to a cycloaddition reaction in the presence of a bifunctional squaramide organocatalyst to afford the desired bispirocycles in high yields and excellent stereoselectivities. Chiral high-performance liquid chromatography (HPLC) is carried out to determine the enantiomeric purity of the products, and the d.r. value is examined by proton nuclear magnetic resonance (1H NMR). The absolute configuration of the product is assigned according to an X-ray crystallographic analysis. This synthetic strategy allows scientists to prepare a diversity of bispirocyclic scaffolds in high yields and excellent diastereo- and enantioselectivities.

Enantiomerically enriched bispiro[&#947;-butyrolactone-pyrrolidin-4,4&#39;-pyrazolone] skeletons are asymmetrically synthesized through a simple organocatalytic 1,3-dipolar cycloaddition reaction.

Verimli α-Imino γ-Lactones Organocatalytic Cycloadditions ve Alkylidene Pirazolonlar ile ilaç gibi Bispirocyclic İskele İnşaatı

Bispirocyclic scaffolds are one of the important structural subunits in many natural products that exhibit diverse and attractive biological activities. ...

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

We introduced a regioselective and atom-economical procedure for the synthesis of 3-substituted indoles by annulation of nitrosoarenes with ethynyl ketones. The reactions were carried out achieving indoles without any catalyst and with excellent regioselectivity. No traces of 2-aroylindole products were detected. Working with 4-nitronitrosobenzene as starting material, the 3-aroyl-N-hydroxy-5-nitroindole products precipitated from the reaction mixtures and were isolated by filtration without any further purification technique. Differently from the corresponding N-hydroxy-3-aryl indoles that, spontaneously in solution, give dehydrodimerization products, the N-hydroxy-3-aroyl indoles are stable and no dimerization compounds were observed.

A Direct, Regioselective and Atom-Economical Synthesis of 3-Aroyl-N-hydroxy-5-nitroindoles by Cycloaddition of 4-Nitronitrosobenzene with Alkynones

3-Aroyl-N-hydroxy-5-nitroindoles were synthesized by cycloaddition of 4-nitronitrosobenzene with a conjugated terminal alkynone in a one-step thermal procedure. Preparation of the nitrosoarene and of the alkynones were adequately reported and respectively through oxidation procedures on the corresponding aniline and on the alkynol.

Alkiyonları ile 4-Nitronitrosobenzene Sikloaddition tarafından 3-Aroyl- N-hidroksi-5-nitroinollerin Direkt, Regiosel ve Atom-Ekonomik Sentezi

We introduced a regioselective and atom-economical procedure for the synthesis of 3-substituted indoles by annulation of nitrosoarenes with ethynyl ...

Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly

This protocol presents the use of Lewis acidic multi-role reagents to circumvent kinetic trapping observed during the self-assembly of information-encoded oligomeric strands mediated by paired dynamic covalent interactions in a manner mimicking the thermal cycling commonly employed for the self-assembly of complementary nucleic acid sequences. Primary amine monomers bearing aldehyde and amine pendant moieties are functionalized with orthogonal protecting groups for use as dynamic covalent reactant pairs. Using a modified automated peptide synthesizer, the primary amine monomers are encoded into oligo(peptoid) strands through solid-phase submonomer synthesis. Upon purification by high-performance liquid chromatography (HPLC) and characterization by electrospray ionization mass spectrometry (ESI-MS), sequence-specific oligomers are subjected to high-loading of a Lewis acidic rare-earth metal triflate which both deprotects the aldehyde moieties and affects the reactant pair equilibrium such that strands completely dissociate. Subsequently, a fraction of the Lewis acid is extracted, enabling annealing of complementary sequence-specific strands to form information-encoded molecular ladders characterized by matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS). The simple procedure outlined in this report circumvents kinetic traps commonly experienced in the field of dynamic covalent assembly and serves as a platform for the future design of robust, complex architectures.

A protocol is presented for the synthesis of information-encoded peptoid oligomers and for the sequence-directed self-assembly of these peptoids into molecular ladders using amines and aldehydes as dynamic covalent reactant pairs and Lewis acidic rare-earth metal triflates as multi-role reagents.

Bilgi taşıyan Peptoidlerin sentezi ve Dizi yönelimli Dinamik Kovalent Öz-montaj

This protocol presents the use of Lewis acidic multi-role reagents to circumvent kinetic trapping observed during the self-assembly of information-encoded ...