This work was supported by the UOIT start-up fund. We thank Mr. Matthew Baxter (UOIT) for his assistance in the laboratory.

Ynone 1. sentezi <ol><li> Bir analitik terazi kullanılarak, istenen potasyum alkynyltrifluoroborate tuzu (1.5 eşdeğer), 0.15 mmol tartın ve bir manyetik karıştırma çubuğu ile donatılmış bir temiz bir viale eklenmektedir. </li><li> Trifloroborat bir 0.3 M çözelti elde şişeye susuz DCM ve 0.5 ml ilave bir iğne ile donatılmış cam bir piston şırınga kullanarak. NOT: Bu bir yeni metodoloji olduğundan, tepkiler kavramının kanıtı için yapılmıştır. Israfı azaltmak amacıyla bir küçük ölçekte yapılmıştır. Reaksiyon gerektiği gibi daha büyük bir verim elde etmek için ölçeklenebilir. </li><li> Bir cam şırınga kullanılarak, karıştırma ile, oda sıcaklığında (20 ° C) &#39;de tepkime kabına 1.0 M bor triklorür çözeltisi 0.15 mmol (1.5 eşdeğer, 150 ul) damla damla ilave edin. Kapağı değiştirin. Tutun veya reaksiyon çözeltisi sonikatörde su sınırının altında olacak şekilde kapatılmış bir reaksiyon kabı kelepçe. 20 ° C&#39;de 30 saniye için bir çözüm, bir frekans o sonikasyonf 40 kHz. </li><li> Ilave bir 20 dakika boyunca, oda sıcaklığında (20 ° C), reaksiyon çözeltisi karıştırılır. Alkynyltrifluoroborate başlangıç ​​malzemesinin niteliğine bağlı olarak, bir renk değişimi dikkate alınmalıdır. Tan beyaz veya kahverengi koyu kırmızı veya mor gelen bir renk değişikliği yaygındır. </li><li> Karıştırma ile çevre sıcaklığında, şişe (20 ° C) uygun bir asil klorür (1.0 eşdeğer) içinde 0.1 mmol ekleyin. Seçenek olarak ise, bir manyetik karıştırma çubuğu ile yüklenmiş bir şişeye, reaksiyon kabının içerikleri transferi ve asil klorit, 0.1 mmol. Kapağı değiştirin. 30 dakika boyunca oda sıcaklığında (20 ° C), reaksiyon çözeltisi karıştırılır. Not: Genellikle, çok koyu renkli bir değişiklik tepkimenin meydana göstergesidir. </li><li> Bir ince tabaka kromatografisi (TLC), 34 kullanılması, uygun asil klorid standartla karşılaştırılması ile tepkime seyrini izler. NOT: Başlangıç ​​malzemelerinin doğasına bağlı olarak, reaksiyon tamamlanmaya kadar olabilir. birsilindir klorit başlangıç ​​malzemesi, bu yöntem kullanılarak bugüne kadar hazırlanan ynones tüm nihai üründen daha yüksek bir çalışma noktası olarak tespit edilmiştir. <ol><li> Küçük bir cam şişe içinde etil asetat, 1 ml başlangıç ​​malzemesinin asil klorür, yaklaşık 10 mg seyreltilmesiyle asil klorid standardı hazırlayın. </li><li> TLC gözcü kullanarak, TLC plakası başlangıç ​​hattı üzerinde reaksiyon çözeltisi ve standart nokta. Reaksiyon çözeltisi ve standardı ile bir ko-nokta yine, reaksiyon çözeltisi içinde mevcut başlangıç ​​materyali olup olmadığını belirlemek için yararlı olabilir. </li><li> Deneme ve yanılma ile uygun bir TLC mobil faz belirleyin. Ürün 1a hazırlanması için, bir mobil faz 01:30 etil asetat içeriği: ynone ürün ve benzoil klorür, yaklaşık 0.5 ve 0.8 Rf değerleri hekzan sonuç, sırasıyla, başlangıç ​​malzemesi. </li><li> UV ışığı altında geliştirilen TLC plakası gözünüzde canlandırın. Herhangi bir görünür noktalar işaretlemek için bir kalem kullanın. </li></ol></li></ol> 2. Sulu Çalıştırma <ol><li> Reaksiyon kabına soğuk su (yaklaşık 5 ° C) bir 1 ml ilave etmek suretiyle reaksiyonu söndürün. Pasteur pipeti kullanılarak, temiz bir ayırma hunisine çözeltisi aktarın. Bundan başka 10 ml soğuk su ile ayırıcılı bir huniye seyreltmek ve 15 ml etil asetat içine bir kez ürünü çıkarmak. </li><li> Alt sulu katman atılır ve 10 ml su ve 10 ml tuzlu sadece bir kez organik katman, bir kez yıkayın. Temiz bir Erlenmeyer şişesi içine Organik tabakayı toplayın ve magnezyum sülfat ile kurutulur. Gravite filtrasyonu kullanılarak temiz bir yuvarlak dipli bir şişeye solüsyonu filtre. </li></ol> Ynone 3. saflaştırılması <ol><li> Ince tabaka kromatografisi kullanarak, ürünün flaş kromatografisi ile arıtılmış, uygun bir mobil faz belirler. Yaklaşık 0.5 bir tutma faktörü (Rf) herhangi bir geri kalan başlangıç ​​ürünü ayırmak için genellikle yeterlidirmateryal ve ürünleri yan ing. Not: ürün, bir daha düşük Rf değerine sahip olduğu düşük ayrılması durumunda, daha az polar bir çözücü sistemi gibi kullanılabilmektedir. 1-5: 30 aralığında etil asetat karışımı: başlangıç ​​malzemeleri, bir heksan polaritesine bağlı olarak 1, genel olarak uygundur. </li><li> Uygun mobil faz ile ıslak bir sütun içeren silis hazırlayın. Ürün ve yıkama sıvısı ilavesi üzerine rahatsız edici bir silis önlemek için kolonun üstüne kum tabakası ekleyin. </li><li> 40 ° C&#39;de banyo sıcaklığında ve 120 rpm&#39;ye ayarlanmış rotasyonu ile bir döner buharlaştırıcı kullanılarak muamele çözeltisi buharlaştırın. Mobil faz 2 ml şişenin içeriğini çözülür ve dikkatle kolon üzerine eşit bir şekilde bir çözüm yerleştirin. Silika ıslak ama çözücü hat silis yüksekliğini aşmayacak emin olun. Bu durum bazı çözgen ürün silika üzerinde olacak şekilde elüte izin verin. Mobil faz ve tekrar bir miktar ekleyin. </li><li> Col doldurunAşama 3.1 belirlenen mobil faz ile UMN; Ürün 1a durumda, 30: 1 heksan: etil asetat karışımı uygundur. Saflaştırma işlemi hızlandırmak için flaş kromatografisi kullanılarak test tüplerinde kesirler toplanır. Basitçe bir hava çıkışına tüp ile bir adaptör bağlayın. Yıkama sıvısı, uygun bir oranda bir sütun üzerinden akacak şekilde hava basıncını ayarlar. </li><li> Bir TLC plakası üzerinde kolon fraksiyonları, her spot. İsteğe bağlı olarak, bir referans olarak asil klorid standart nokta. Mobil faz aşamasında 1.8 uygun gördüğü kullanarak TLC geliştirin. Ürün asil klorür standardından daha düşük R f olması bekleniyor belirterek, UV ışık altında görülebilen noktalar işaretleyin. </li><li> Büyük bir yuvarlak tabanlı bir şişe içine görünür lekeler içeren tüm fraksiyonlar toplanır. Başlangıç ​​malzemesi daha düşük Rf birden fazla nokta mevcut ise, ayrı şişeler içerisinde toplamak. Bir döner buharlaştırıcı kullanılarak çözücü buharlaştırılmakta ve unde toplanan malzemenin kuruiki saat boyunca yüksek vakum r. </li><li> Eğer gerekirse, bundan başka, bir elektron zayıf asil klorid başlangıç ​​malzemesinden hazırlanan bir ynone ürünün arıtılması için küçük bir sütun üzerinde pentan yıkama yapar. Küçük bir skala üzerinde bu, kolonu gibi bir Pasteur pipeti kullanılarak gerçekleştirilebilir. <ol><li> Pentan ile ıslak bir silis kolonu üzerine kloroform, DCM veya dietil eter ve yükün bir minimum ürün çözülür. Zehir 1-2 sütun sütun aracılığıyla pentan uzunlukları ve atık beher içine toplamak. </li><li> Dietil eter ya da etil asetat kullanılarak pentan sütun saf ynone ürünü elute edin. Ayrı bir şişe içinde eluent toplamak buharlaşması ve iki saat içinde en az yüksek vakum altında yerleştirin. NMR spektroskopisi ile karakterize ürünün yaklaşık 10 mg elde edilir. </li></ol></li></ol> Ynone 4. karakterizasyonu <ol><li> Karakterize 1 H ve 13C NMR spektroskopisi kullanarak nihai ürünün saflığını değerlendirmek. 34Tipik olarak, karbonil karbon kimyasal kayma 13C NMR spektrum 177 ppm yakın görünür. ynone fonksiyonel grubun her iki SP karbon 87 ve 93 ppm yakınında karakteristik zirveleri ile temsil edilmektedir. </li><li> Ynone ürünün karakteristik karbonil tepe noktasını belirleyebilir, kızılötesi spektroskopi 34 kullanın. Komşu üçlü bağ elektron delokalizasyon genellikle karbonil zirve 1.600 ila 1.650 cm görünmesini -1, bileşiğin elektronik özelliklerine bağlı olarak neden olur. </li><li> Ürünün moleküler kütlesi belirlemek ve daha yüksek çözünürlüklü kütle spektrometrisi kullanılarak kimlik doğrulama. 34 </li></ol>

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W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Amide&#8208;Forming+Ligation+of+Acyltrifluoroborates+and+Hydroxylamines+in+Water.">Amide&#8208;Forming Ligation of Acyltrifluoroborates and Hydroxylamines in Water.</a> Angew. Chem. Int. Ed. 51, 5683-5686 (2012).</li><li>Mitchell, T. A., Bode, J. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+Dialkyl+Ethers+from+Organotrifluoroborates+and+Acetals.">Synthesis of Dialkyl Ethers from Organotrifluoroborates and Acetals.</a> J. Am. Chem. Soc. 131, 18057-18059 (2009).</li><li>Vo, C. -. V. T., Mitchell, T. A., Bode, J. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Expanded+substrate+scope+and+improved+reactivity+of+ether-forming+cross-coupling+reactions+of+organotrifluoroborates+and+acetals.">Expanded substrate scope and improved reactivity of ether-forming cross-coupling reactions of organotrifluoroborates and acetals.</a> J. Am. Chem. Soc. 133, 14082-14089 (2011).</li><li>Zeng, J., Vedachalam, S., Xiang, S., Liu, X. -. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+C-Glycosylation+of+Organotrifluoroborates+with+Glycosyl+Fluorides+and+Its+Application+to+the+Total+Synthesis+of+(+)-Varitriol.">Direct C-Glycosylation of Organotrifluoroborates with Glycosyl Fluorides and Its Application to the Total Synthesis of (+)-Varitriol.</a> Org. Lett. 13, 42-45 (2010).</li><li>Lehman, J. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+student's+lab+companion:+laboratory+techniques+for+organic+chemistry:+standard+scale+and+microscale.">The student's lab companion: laboratory techniques for organic chemistry: standard scale and microscale.</a> Pearson College Div. , (2008).</li><li>Molander, G. A., Cavalcanti, L. N., Canturk, B., Pan, P. -. S., Kennedy, L. E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Efficient+Hydrolysis+of+Organotrifluoroborates+via+Silica+Gel+and+Water.">Efficient Hydrolysis of Organotrifluoroborates via Silica Gel and Water.</a> 74, 7364-7369 (2009).</li><li>Molander, G. A., Ellis, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Organotrifluoroborates:+protected+boronic+acids+that+expand+the+versatility+of+the+Suzuki+coupling+reaction.">Organotrifluoroborates: protected boronic acids that expand the versatility of the Suzuki coupling reaction.</a> Acc. Chem. Res. 40, 275-286 (2007).</li><li>Calloway, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Friedel-Crafts+Syntheses.">The Friedel-Crafts Syntheses.</a> Chem. Rev. 17, 327-392 (1935).</li><li>Gore, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Friedel-Crafts+acylation+reaction+and+its+application+to+polycyclic+aromatic+hydrocarbons.">The Friedel-Crafts acylation reaction and its application to polycyclic aromatic hydrocarbons.</a> Chem. Rev. 55, 229-281 (1955).</li><li>Groves, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Friedel&#8211;Crafts+acylation+of+alkenes.">The Friedel&#8211;Crafts acylation of alkenes.</a> Chem. Soc. Rev. 1, 73-97 (1972).</li><li>Kim, B. J., Matteson, D. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Conversion+of+alkyltrifluoroborates+into+alkyldichloroboranes+with+tetrachlorosilane+in+coordinating+solvents.">Conversion of alkyltrifluoroborates into alkyldichloroboranes with tetrachlorosilane in coordinating solvents.</a> Angew. Chem. 116, 3118-3120 (2004).</li><li>Thompson, L., Doraiswamy, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Sonochemistry:+science+and+engineering.">Sonochemistry: science and engineering.</a> Ind. Eng. Chem. Res. 38, 1215-1249 (1999).</li></ol>

The authors declare that they have no competing financial interests.

Tablo 1, tekabül eden ynone ürünü oluşturmak üzere benzoil klorid ile fenilasetilen trifloroborat reaksiyonu koşulları optimize etmek için alınan adımları göstermektedir. Başlangıçta, organodifluoroboranes için organotrifluoroborates dönüştürmek için bilinen katalizörler test edilir. Ne yazık ki silika jel, 35 silikon tetraklorür, 36 ve bor trifluorür 31,32 istenen ynone oluşumunu (Tablo 1, girişleri 1-3) teşvik etmedi. kanıtladı klorlu Lewis asidi katalizör kullanımı daha başarılı olmak için. İstenen ynone 1a düşük verimli bir demir (III) klorür katalizörün (Tablo 1, giriş 4) mevcudiyetinde elde edildi. Daha sonra, alüminyum (III) klorür, Friedel-Crafts açillemeler olarak oxocarbenium iyonu oluşumunu teşvik etmek için, iyi kurulmuş yeteneğinin bir sonucu olarak incelenmiştir., Bir alüminyum (III) klorür katalizörün zaman 37-39 istenen ürün% 62 verim ile elde edildi employed. Daha fazla optimizasyon hava ve nem tepkimenin veriminde (Tablo 1, girişleri 5-7) üzerinde çok az bir etkiye sahip olduğunu göstermektedir. Bunun bir sonucu olarak, daha sonraki reaksiyonlar hava varlığında olmayan kurutulmuş cam malzemede gerçekleştirildi. Çözücünün optimize etmek için girişimler diklorometan (DCM) reaksiyonu (Tablo 1, girişleri 8-12) için özellikle uygun olduğunu göstermiştir. Alüminyum (III) klorür ile katalize edilen reaksiyonlara sonuçlarında tutarsızlıklar alternatif katalizörlerin araştırılmasını teşvik. Ticari olarak elde edilebilen alüminyum (III) klorür heksahidrat, reaksiyon koşulları altında (Tablo 1, giriş 13) altında tamamen etkisizdi. Bu alüminyum (III) klorür hidrat oluşturma reaksiyonunu inhibe ettiği iyi bir göstergesidir. Bor triklorür daha tutarlı (Tablo 1, giriş 14) benzer verimler elde etmek için bulunmuştur. Potasyum alkynyltriflu etkileşimi üzerinebor triklorürle oroborate, daha reaktif organodichloroborane türleri oluşturulmuştur. 40 Bu ilk aşama devam etmek ynone asil klorür ve oluşumu ile reaksiyon için kritik önem taşır. Organotrifluoroborate edilebilir tuzları, DCM içinde çözünür olmadığı için, reaksiyon, heterojen bir karışım olarak gerçekleşir. Bor triklorür ilave edildikten sonra çözelti, reaksiyon için uygun trifloroborat tuzu, yüzey alanını arttırarak, reaktif dichloroborane türlerinin oluşumunun kolaylaştırılması için ses dalgalarına tabi tutulur. Reaksiyon karışımına ultrason dalgalarının uygulama kavitasyon kabarcıklarının hasıl edilmesi ile mekanik etkilere neden olmaktadır. Sonikasyonun sırasında, kavitasyon çöküşü, yüksek sıcaklık ve basınç yerelleştirilmiş alanlarında sıvı sonuçlar kabarcıkları. 41 Şok dalgaları katı trifloroborat tuzlarının kinetik enerji bir artışa neden mikroskobik türbülans oluşturmak üretilmektedir. Sonication promo sırasında sistemin enerji artıştrifloroborat tuzu TES parçalanma bor triklorür ile etkileşim için uygun olan yüzey alanının arttırılmasını elde. Önce asil klorid başlangıç ​​malzemesi ilavesinden tepkime karışımın sonikasyonu daha zorlayıcı koşullar veya daha uzun reaksiyon süreleri için gerek kalmadan reaktif alkynyldichloroborane türlerin verimli oluşumunu sağlar. Şekil 2, fenilasetilen trifloroborat optimum reaksiyon koşulları altında, asil klorürler, çeşitli ile reaksiyona sokuldu zaman elde edilen sonuçlar gösterilmektedir. Nötr aromatik (1b, 1c) ve alifatik (1 i-l), asil klorürler, sentetik olarak yararlı verimlerle gelen ynones vermek. Elektron çeken gruplar nispeten mütevazı verimleri (1h, 1i, 1m) neden olurken elektron verici gruplar (1d-g) taşıyan bu asil klorürler mükemmel verimi sağlamak. Intereelektron çekici grup orto konumunda (1i,% 59) bulunduğu zaman stingly, önemli bir verim artışı benzer para olan karşılaştırılması görülmektedir asil klorür (1h,% 30) ikame edilebilir. orto konumunda ikame sterik etkileşim böylece bir aromatik halkanın bir elektron çekme karakteri dengelemek, düzleminden dışarı karbonil grubu zorlayabilir. Bu 4-bromobutirilbromid klorür% 39 verimle istenen ürün 1m göze tepki dikkati çekiyor. Bildiğimiz kadarıyla, bu bir alkil bromür fonksiyonel grubu tolere ynones sentezi için, ilk bir protokoldür. Başlangıç ​​malzemesi asil klorür nötr veya elektron eksik olduğunda Bazen, alifatik kirlilikler proton NMR görünür. Bu durum, ürünün arıtılması için bir pentan yıkama gerektirebilir. Mümkün iken, ilk arıtma aşaması s sırasında pentan yıkama gerçekleştirmek için ekonomik değildirince pentan, hekzan ile karşılaştırıldığında maliyetlidir. Böyle bir Pasteur pipeti kolonu gibi daha küçük bir ölçekte ayrı olarak ikinci bir arıtma işleminin tamamlanması önemli ölçüde gerekli pentan miktarını azaltır. Şekil 3, reaksiyonun verimi üzerine alkynyltrifluoroborate tuzu kimlik etkisini göstermektedir. Genel olarak, bir aromatik halka üzerinde bir fenilasetilen trifloroborat tuzu taşıyan bir elektron verici ikame türevleri mükemmel verimler (2a-c, 3a-c) iyi istenen ynones üretilmesi için aromatik ve alifatik asil klorürler ile reaksiyona sokulmuştur. Alifatik alkynyltrifluoroborate tuzlan daha az reaktif substratlar olduğunu kanıtladı. Hexynyl- ve cyclopentylethynyltrifluoroborate tuzlan elektron açısından zengin bir benzoil klorür türevleri (4a, 5a) ile reaksiyona sokuldu zaman mütevazı verimler elde edilmiştir. Sonuç olarak, hazırlama O için yeni bir yöntemle def asil klorür ve potasyum alkynyltrifluoroborate tuzlarından ynones geliştirilmiştir. mütevazı gelen asil klorür doğasına bağlı olarak iyi bu yöntem aralığının ile ynones sentezi için elde edilen sonuçlar ve başlangıç ​​maddeleri trifloroborat. Genel olarak, elektron verici ikame edicilerine sahip olanlar başlangıç ​​malzemeleri, nötr ve elektron çekici fonksiyonel grupları taşıyan başlangıç ​​malzemeleri daha kolay tepkimeye girerler. Bu yaklaşımın değeri yöntemin operasyon kolaylığı ve fonksiyonel grup tolerans yer alır. Bu basit, tek-kaplı bir reaksiyonun hava ve nem hariç tutulmaksızın bor triklorür varlığında, oda sıcaklığında hızlı bir şekilde ilerler. Bu uygun yöntem asil klorürler ve alkynyltrifluoroborate tuzlarının çeşitli mükemmel verimler mütevazı olarak ynones hazırlanmasında kullanılabilir.

The intention of this video is to demonstrate a straightforward approach for the preparation of compounds containing an ynone functional group from convenient starting materials. Ynones are valuable building blocks in organic chemistry that have been shown to have biomedical and material significance. Ynones are precursors to valuable organic functional groups including pyrimidines,1,2 quinolones,3 furans,4 pyrazoles,5,6 flavones,7 oximes,8 and chiral propargylic alcohols.9-11 A more convenient method for the preparation of ynones has been sought as a result of the drawbacks of traditional methods including poor functional group tolerance and tedious synthetic routes.
The reaction of metal12,13 and metalloid14 acetylides with acyl chlorides is one common route for the preparation of ynones. Alternatively, the synthesis of ynones from acyl chloride can be achieved via two-step procedures using Weinreb amides and organolithium or Grignard reagents.15 Another prevalent approach includes the addition of organolithium or Grignard reagents to an aldehyde, which is followed by the oxidation of a secondary alcohol to the corresponding ketone.16-19 Poor functional group tolerance of metal acetylides and the need to purify synthetic intermediates after each step are main deficiencies of the aforementioned methods. Transition-metal-catalyzed carbonylative couplings have recently emerged as an alternative approach for the preparation of ynones.20-22 Unfortunately, in addition to cost and toxicity associated with transition metals, metal-catalyzed carbonylative reactions often require elevated CO pressures and suffer from the presence of an undesired Sonogashira coupling byproduct. Given their utility in organic synthesis as well as the drawbacks associated with traditional synthetic methods, the development of a more straightforward method for the preparation of ynones is appealing.
Potassium organotrifluoroborate salts have recently emerged as versatile reagents in organic synthesis. Advantages including ease of preparation,23 inherent stability, low toxicity, and good functional group tolerance have made organotrifluoroborate salts attractive synthetic reagents.24-27 Organotrifluoroborate salts have been used primarily as a bench-stable equivalent of boronic acids for palladium-catalyzed Suzuki-Miyaura coupling.26 Recently, following a seminal work by Matteson and co-workers,28 Bode, Molander and others have highlighted the utility of organotrifluoroborates as reagents in non-metal catalyzed reactions.29-33 The field of transition-metal-free reactions of trifluoroborates is still in its infancy stage. Given the great potential for use of organotrifluoroborate salts in non-metal catalyzed organic synthesis, we sought to develop a novel method for the preparation of ynones from acyl chlorides and alkynyltrifluoroborate salts.

<table border="0" cellpadding="0" cellspacing="0" width="573">
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Name of Material/ Equipment</td>
			<td style="width:71px;">Company</td>
			<td style="width:119px;">Catalog Number</td>
			<td style="width:167px;">Comments/Description</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Sonicator</td>
			<td style="width:71px;">VGT</td>
			<td style="width:119px;">1860QT</td>
			<td>Ultrasonic cleaner. Similar sonication devices may be used.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Dichloromethane</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">270997</td>
			<td>Anhydrous</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Boron trichloride solution&#160;</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">178934</td>
			<td>1M solution in DCM</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Acyl chloride</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">Various</td>
			<td>Acyl chlorides from other suppliers such as Alfa Aesar may be used. Caution - refer to MSDS for safety information.</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Potassium alkynyltrifluoroborate salt</td>
			<td style="width:71px;">N/A</td>
			<td style="width:119px;">N/A</td>
			<td>Synthesized23 from terminal alkyne</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Ethyl acetate</td>
			<td style="width:71px;">ACP</td>
			<td style="width:119px;">E-2000</td>
			<td>ACS grade</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Hexanes</td>
			<td style="width:71px;">ACP</td>
			<td style="width:119px;">H-3500</td>
			<td>ACS grade</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Pentane</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">236705</td>
			<td>Anhydrous</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Magnesium sulfate</td>
			<td style="width:71px;">Sigma</td>
			<td style="width:119px;">M7506</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Filter paper</td>
			<td style="width:71px;">Whatman</td>
			<td style="width:119px;">1093 126</td>
			<td>Student grade. This speceific variety is not necessary.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">Silica Gel 60</td>
			<td style="width:71px;">EMD</td>
			<td style="width:119px;">1.11567.9026</td>
			<td>Particle size 0.040-0.063</td>
		</tr>
	</tbody>
</table>

metal-free synthesis of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts

Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups and scaffolds. Traditional methods for the preparation of ynones are associated with drawbacks including harsh conditions, multiple purification steps, and the presence of unwanted byproducts. An alternative method for the straightforward preparation of ynones from acyl chlorides and potassium alkynyltrifluoroborate salts is described herein. The adoption of organotrifluoroborate salts as an alternative to organometallic reagents for the formation of new carbon-carbon bonds has a number of advantages. Potassium organotrifluoroborate salts are shelf stable, have good functional group tolerance, low toxicity, and a wide variety are straightforward to prepare. The title reaction proceeds rapidly at ambient temperature in the presence of a Lewis acid without the exclusion of air and moisture. Fair to excellent yields may be obtained via reaction of various aryl and alkyl acid chlorides with alkynyltrifluoroborate salts in the presence of boron trichloride.

Ilk çabalar fenilasetilen trifloroborat S1 ve benzoil klorür (Şekil 1) gelen ynone 1a hazırlanması üzerine odaklanmıştır. Tablo 1 optimizasyon adımları çeşitli Lewis asitleri, çözücüler ve aynı zamanda reaksiyon su etkisinin incelenmesi taranması dahil gerçekleştirilir görüntülemektedir . Daha sonra, tepkime kapsamının asil klorürler çeşitli mevcudiyetinde (Şekil 2) optimize edilmiş koşullar fenilasetilen trifloroborat göndererek incelenmiştir. Mükemmel verimler ile mütevazı asil klorid alt-tabakanın doğasına bağlı olarak elde edilebilir. Reaksiyonun kapsamı daha alkynyltrifluoroborate tuzlarının çeşitli ek örnekleri hazırlanması suretiyle değerlendirilmiştir. 3 gelişmiş koşullar altında ynones hazırlanmasında kullanılabilir diğer alkynyltrifluoroborate tuzların seçilen örnekleri göstermektedir, Şekil. Phen türevlerialkynyltrifluoroborate tuzların alifatik türevleri biraz daha az reaktif verecek mütevazı getirileri olduğunu kanıtladı ise mükemmel verimler iyi karşılık gelen ynone ürünleri tanınan ikame ediciler bağış trifloroborat yatak elektron ylacetylene. <img alt="Şekil 1," src="/files/ftp_upload/52401/52401fig1highres.jpg" /> Şekil 1:. Reaktif ara madde dichloroborane oluşumu da dahil olmak üzere ynone 1a hazırlanması için koşullarını gösteren fenilasetilen trifloroborat S1 ve benzoil klorür Şema gelen Ynone 1a hazırlanması. <img alt="Şekil 2," src="/files/ftp_upload/52401/52401fig2highres.jpg" /> Şekil 2:. Ynone 1a Örnek 1 &#39;H-NMR spektrumu Kimyasal kaymalar ve karakteristik protonların görece entegrasyonlar etiketlenir. Şekil 3:. Ynone 1a Örnek 13C NMR spektrumu karakteristiği karbonlu Kimyasal kaymalar etiketlenir. <img alt="Şekil 4," src="/files/ftp_upload/52401/52401fig4highres.jpg" /> Şekil 4:. Atmosferik basınçta kimyasal iyonizasyon yoluyla elde ynone 1a Örnek HRMS spektrumu [M + H] ölçülen m / z değeri + iyonu bildirilmektedir. <img alt="Şekil 5," src="/files/ftp_upload/52401/52401fig5highres.jpg" /> Şekil 5: kimliği değiştirilerek üretilen ürünler için asil klorürler ile phenylacetylenetrifluoroborate tuzu S1 Reaksiyonları Yapıları ve verimleri.asil klorür başlangıç ​​malzemesinin görüntülenmiştir. Reaksiyonlar asil kloridin 1 eşdeğer, 1.5 eşdeğer potasyum phenylacetylenetrifluoroborate S1 ve 1.5 eşdeğer bor triklorür ile elde edildi. <img alt="Şekil 6," src="/files/ftp_upload/52401/52401fig6highres.jpg" /> Şekil 6:. Asil klorürler Yapılar ve alkynyltrifluoroborate başlangıç ​​malzemesinin kimliği değiştirilerek üretilen ürünlerin verimi çeşitli alkynyltrifluoroborates reaksiyonları tasvir edilmiştir. Reaksiyonlar asil kloridin 1 eşdeğer, 2.5 eşdeğer potasyum organotrifluoroborate tuzu ve 2.5 eşdeğer bor triklorür ile elde edildi. <table border="0" cellpadding="0" cellspacing="0"><tbody><tr><td> Giriş </td><td> Lewis asidi </td><td> Lewis asidi (eşdeğer) </td><td> Koşullar </td><td> Yol Ver (%) </td></tr><tr><td> 1 b &lt;/ Sup&gt; </td><td> SiO 2 </td><td> 16.5 </td><td> CH2C! 2 </td><td> 0 </td></tr><tr><td> 2 </td><td> SiCl 4 </td><td> 1 </td><td> CH2C! 2 </td><td> iz </td></tr><tr><td> 3 </td><td> BF 3 · OEt&#39;dir 2 </td><td> 1 </td><td> CH2C! 2 </td><td> iz </td></tr><tr><td> 4 b </td><td> FeCl3 </td><td> 1 </td><td> CH2C! 2 </td><td> 24 </td></tr><tr><td> 5 C </td><td> AICI3 </td><td> 1 </td><td> CH2C! 2 </td><td> 62 </td></tr><tr><td> 6 d </td><td> AICI3 </td><td> 1 </td><td> CH2C! 2 </td><td> 66 </td></tr><tr><td> 7 E </td><td> AICI3 </td><td> 1 </td><td> CH2C! 2 </td><td> 60 </td></tr><tr><td> 8 </td><td> AICI3 </sub&gt; </td><td> 1 </td><td> THF </td><td> iz </td></tr><tr><td> 9 </td><td> AICI3 </td><td> 1 </td><td> tolüen </td><td> iz </td></tr><tr><td> 10 </td><td> AICI3 </td><td> 2 </td><td> ClCH 2 CH2Ch </td><td> 33 </td></tr><tr><td> 11 </td><td> AICI3 </td><td> 1 </td><td> DMSO </td><td> iz </td></tr><tr><td> 12 </td><td> AICI3 </td><td> 2 </td><td> asetonitril </td><td> iz </td></tr><tr><td> 13 </td><td> AICI3 · 6H 2 O </td><td> 1 </td><td> CH2C! 2 </td><td> 0 </td></tr><tr><td> 14 b </td><td> BCl 3 </td><td> 1.5 </td><td> CH2C! 2 </td><td> 67 </td></tr><tr><td> 15 </td><td> BBr3 </td><td> 1 </td><td> CH2C! 2 </td><td> 20 </td></tr></tbody></table><strong&gt; Tablo 1:. Ürünün ynone 1a a hazırlanması için koşulların optimum hale getirilmesi Verim Reaksiyon koşulları ve Lewis asidi katalizör değişimi üzerine 1a. Bir Tepkimeler 1 eşdeğer benzoil klorür ve 1 eşdeğer potasyum phenylacetylenetrifluoroborate S1 ile elde edildi. 1.5 eşdeğer S1 b c. Susuz koşullar d. Reaksiyon hava altında olmayan kurutulmuş cam malzemede gerçekleştirildi. E Susuz koşullar + su 1 ul.

Watch this Scientific Journal Video about Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts at JoVE.com

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

The goal of this manuscript is to demonstrate a straightforward method for the preparation of ynones from acyl chloride and potassium alkynyltrifluoroborate salt starting materials. The one-pot reaction proceeds rapidly in the presence of boron trichloride without exclusion of air and moisture.

Asil klorür ve potasyum Alkynyltrifluoroborate Tuzlarından Ynones Metal içermeyen sentezi

Ynones are a valuable functional group and building block in organic synthesis. Ynones serve as a precursor to many important organic functional groups ...

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11.1K Görüntüleme.  University of Ontario Institute of Technology. The goal of this manuscript is to demonstrate a straightforward method for the preparation of ynones from acyl chloride and potassium alkynyltrifluoroborate salt starting materials. The one-pot reaction proceeds rapidly in the presence of boron trichloride without exclusion of air and moisture.

Video: Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

Preparation and Use of Samarium Diiodide (SmI2) in Organic Synthesis: The Mechanistic Role of HMPA and Ni(II) Salts in the Samarium Barbier Reaction

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of molecular iodine to samarium metal in THF.1,2-3 It is a mild and selective single electron reductant and its versatility is a result of its ability to initiate a wide range of reductions including C-C bond-forming and cascade or sequential reactions. SmI2 can reduce a variety of functional groups including sulfoxides and sulfones, phosphine oxides, epoxides, alkyl and aryl halides, carbonyls, and conjugated double bonds.2-12 One of the fascinating features of SmI-2-mediated reactions is the ability to manipulate the outcome of reactions through the selective use of cosolvents or additives. In most instances, additives are essential in controlling the rate of reduction and the chemo- or stereoselectivity of reactions.13-14 Additives commonly utilized to fine tune the reactivity of SmI2 can be classified into three major groups: (1) Lewis bases (HMPA, other electron-donor ligands, chelating ethers, etc.), (2) proton sources (alcohols, water etc.), and (3) inorganic additives (Ni(acac)2, FeCl3, etc).3
Understanding the mechanism of SmI2 reactions and the role of the additives enables utilization of the full potential of the reagent in organic synthesis. The Sm-Barbier reaction is chosen to illustrate the synthetic importance and mechanistic role of two common additives: HMPA and Ni(II) in this reaction. The Sm-Barbier reaction is similar to the traditional Grignard reaction with the only difference being that the alkyl halide, carbonyl, and Sm reductant are mixed simultaneously in one pot.1,15 Examples of Sm-mediated Barbier reactions with a range of coupling partners have been reported,1,3,7,10,12 and have been utilized in key steps of the synthesis of large natural products.16,17 Previous studies on the effect of additives on SmI2 reactions have shown that HMPA enhances the reduction potential of SmI2 by coordinating to the samarium metal center, producing a more powerful,13-14,18 sterically encumbered reductant19-21 and in some cases playing an integral role in post electron-transfer steps facilitating subsequent bond-forming events.22 In the Sm-Barbier reaction, HMPA has been shown to additionally activate the alkyl halide by forming a complex in a pre-equilibrium step.23
Ni(II) salts are a catalytic additive used frequently in Sm-mediated transformations.24-27 Though critical for success, the mechanistic role of Ni(II) was not known in these reactions. Recently it has been shown that SmI2 reduces Ni(II) to Ni(0), and the reaction is then carried out through organometallic Ni(0) chemistry.28
These mechanistic studies highlight that although the same Barbier product is obtained, the use of different additives in the SmI2 reaction drastically alters the mechanistic pathway of the reaction. The protocol for running these SmI2-initiated reactions is described.

Preparation and Use of Samarium Diiodide SmI2 in Organic Synthesis: The Mechanistic Role of HMPA and NiII Salts in the Samarium Barbier Reaction

A straightforward procedure for the preparation of samarium diiodide (SmI2) in THF is described. The role of two main additives namely hexamethylphosphoramide (HMPA) and Ni(acac)2 in Sm mediated reactions is demonstrated in the Sm-Barbier reaction.

Hazırlanması ve Samaryum Diiodide Kullanımı (SMI<sub&gt; 2</sub&gt;) In Organic Synthesis: Samaryum Barbier Reaksiyonu HMPA ve Ni (II) tuzlarının Mekanistik Rolü

Although initially considered an esoteric reagent, SmI2 has become a common tool for synthetic organic chemists. SmI2 is generated through the addition of ...

Kimya

Nucleoside Triphosphates - From Synthesis to Biochemical Characterization

The traditional strategy for the introduction of chemical functionalities is the use of solid-phase synthesis by appending suitably modified phosphoramidite precursors to the nascent chain. However, the conditions used during the synthesis and the restriction to rather short sequences hamper the applicability of this methodology. On the other hand, modified nucleoside triphosphates are activated building blocks that have been employed for the mild introduction of numerous functional groups into nucleic acids, a strategy that paves the way for the use of modified nucleic acids in a wide-ranging palette of practical applications such as functional tagging and generation of ribozymes and DNAzymes. One of the major challenges resides in the intricacy of the methodology leading to the isolation and characterization of these nucleoside analogues.
	
	In this video article, we present a detailed protocol for the synthesis of these modified analogues using phosphorous(III)-based reagents. In addition, the procedure for their biochemical characterization is divulged, with a special emphasis on primer extension reactions and TdT tailing polymerization. This detailed protocol will be of use for the crafting of modified dNTPs and their further use in chemical biology.

The protocol described herein aims to explain and abridge the numerous obstacles in the way of the intricate route leading to modified nucleoside triphosphates. Consequently, this protocol facilitates both the synthesis of these activated building-blocks and their availability for practical applications.

Nükleosid trifosfatlar - sentezinden Biyokimyasal Karakterizasyonu için

The  traditional strategy for the introduction of chemical functionalities is the  use of solid-phase synthesis by appending suitably modified ...

Synthesis and Characterization of Supramolecular Colloids

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

A protocol for the synthesis and characterization of colloids coated with supramolecular moieties is described. These supramolecular colloids undergo self-assembly upon the activation of the hydrogen-bonds between the surface-anchored molecules by UV-light.

Supramoleküler Kolloidlerin Sentezi ve Karakterizasyonu

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical ...

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. Detailed and generalized protocols are also presented for testing the catalytic activity of such complexes in arylation and Suzuki-Miyaura cross-coupling reactions. Representative results are shown for the catalytic activity of the four complexes in arylation and Suzuki-Miyaura type reactions. For each of the reactions investigated, at least one of the four complexes successfully catalyzed the reaction, qualifying them as promising candidates for catalysis of many carbon-carbon bond-forming reactions. The protocols presented are general enough to be adapted for the synthesis, purification and catalytic activity testing of new palladium N-heterocyclic carbene complexes.

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from benzimidazolium salts. The complexes were tested for catalytic activity in arylation and Suzuki-Miyaura reactions. For each reaction investigated, at least one of the four complexes successfully catalyzed the reaction.

palladyum<em&gt; K</em&gt; -Heterosiklik Karben Kompleksleri: Benzimidazolyum Tuzlarından Sentez ve Karbon-karbon Bağ Oluşturma Reaksiyonlarında Katalitik Aktivite

Detailed and generalized protocols are presented for the synthesis and subsequent purification of four palladium N-heterocyclic carbene complexes from ...

Synthesis and Mass Spectrometry Analysis of Oligo-peptoids

Peptoids are sequence-controlled peptide-mimicking oligomers consisting of N-alkylated glycine units. Among many potential applications, peptoids have been thought of as a type of molecular information storage. Mass spectrometry analysis has been considered the method of choice for sequencing peptoids. Peptoids can be synthesized via solid phase chemistry using a repeating two-step reaction cycle. Here we present a method to manually synthesize oligo-peptoids and to analyze the sequence of the peptoids using tandem mass spectrometry (MS/MS) techniques. The sample peptoid is a nonamer consisting of alternating N-(2-methyloxyethyl)glycine (Nme) and N-(2-phenylethyl)glycine (Npe), as well as an N-(2-aminoethyl)glycine (Nae) at the N-terminus. The sequence formula of the peptoid is Ac-Nae-(Npe-Nme)4-NH2, where Ac is the acetyl group. The synthesis takes place in a commercially available solid-phase reaction vessel. The rink amide resin is used as the solid support to yield the peptoid with an amide group at the C-terminus. The resulting peptoid product is subjected to sequence analysis using a triple-quadrupole mass spectrometer coupled to an electrospray ionization source. The MS/MS measurement produces a spectrum of fragment ions resulting from the dissociation of charged peptoid. The fragment ions are sorted out based on the values of their mass-to-charge ratio (m/z). The m/z values of the fragment ions are compared against the nominal masses of theoretically predicted fragment ions, according to the scheme of peptoid fragmentation. The analysis generates a fragmentation pattern of the charged peptoid. The fragmentation pattern is correlated to the monomer sequence of the neutral peptoid. In this regard, MS analysis reads out the sequence information of the peptoids.

A protocol is described for the manual synthesis of oligo-peptoids followed by sequence analysis by mass spectrometry.

Sentez ve kütle spektrometresi analizleri Oligo-peptoids

Peptoids are sequence-controlled peptide-mimicking oligomers consisting of N-alkylated glycine units. Among many potential applications, peptoids have ...

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. ...

Synthesis of Substrate-Bound Au Nanowires Via an Active Surface Growth Mechanism

Advancing synthetic capabilities is important for the development of nanoscience and nanotechnology. The synthesis of nanowires has always been a challenge, as it requires asymmetric growth of symmetric crystals. Here, we report a distinctive synthesis of substrate-bound Au nanowires. This template-free synthesis employs thiolated ligands and substrate adsorption to achieve the continuous asymmetric deposition of Au in solution at ambient conditions. The thiolated ligand prevented the Au deposition on the exposed surface of the seeds, so the Au deposition only occurs at the interface between the Au seeds and the substrate. The side of the newly deposited Au nanowires is immediately covered with the thiolated ligand, while the bottom facing the substrate remains ligand-free and active for the next round of Au deposition. We further demonstrate that this Au nanowire growth can be induced on various substrates, and different thiolated ligands can be used to regulate the surface chemistry of the nanowires. The diameter of the nanowires can also be controlled with mixed ligands, in which another &#34;bad&#34; ligand could turn on the lateral growth. With the understanding of the mechanism, Au nanowire-based nanostructures can be designed and synthesized.

We report a solution-based method to synthesize substrate-bound Au nanowires. By tuning the molecular ligands used during the synthesis, the Au nanowires can be grown from various substrates with different surface properties. Au nanowire-based nanostructures can also be synthesized by adjusting the reaction parameters.

Substrat bağlı Au Nanowires bir aktif yüzey büyüme mekanizması yoluyla sentezi

Advancing synthetic capabilities is important for the development of nanoscience and nanotechnology. The synthesis of nanowires has always been a ...

Synthesis and Characterization of Amphiphilic Gold Nanoparticles

Gold nanoparticles covered with a mixture of 1-octanethiol (OT) and 11-mercapto-1-undecane sulfonic acid (MUS) have been extensively studied because of their interactions with cell membranes, lipid bilayers, and viruses. The hydrophilic ligands make these particles colloidally stable in aqueous solutions and the combination with hydrophobic ligands creates an amphiphilic particle that can be loaded with hydrophobic drugs, fuse with the lipid membranes, and resist nonspecific protein adsorption. Many of these properties depend on nanoparticle size and the composition of the ligand shell. It is, therefore, crucial to have a reproducible synthetic method and reliable characterization techniques that allow the determination of nanoparticle properties and the ligand shell composition. Here, a one-phase chemical reduction, followed by a thorough purification to synthesize these nanoparticles with diameters below 5 nm, is presented. The ratio between the two ligands on the surface of the nanoparticle can be tuned through their stoichiometric ratio used during synthesis. We demonstrate how various routine techniques, such as transmission electron microscopy (TEM), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), and ultraviolet-visible (UV-Vis) spectrometry, are combined to comprehensively characterize the physicochemical parameters of the nanoparticles.

Amphiphilic gold nanoparticles can be used in many biological applications. A protocol to synthesize gold nanoparticles coated by a binary mixture of ligands and a detailed characterization of these particles is presented.

Amphiphilik altın nanopartiküller sentezi ve karakterizasyonu

Gold nanoparticles covered with a mixture of 1-octanethiol (OT) and 11-mercapto-1-undecane sulfonic acid (MUS) have been extensively studied because of ...

Hierarchical and Programmable One-Pot Oligosaccharide Synthesis

This article presents a general experimental protocol for programmable one-pot oligosaccharide synthesis and demonstrates how to use Auto-CHO software for generating potential synthetic solutions. The programmable one-pot oligosaccharide synthesis approach is designed to empower fast oligosaccharide synthesis of large amounts using thioglycoside building blocks (BBLs) with the appropriate sequential order of relative reactivity values (RRVs). Auto-CHO is a cross-platform software with a graphical user interface that provides possible synthetic solutions for programmable one-pot oligosaccharide synthesis by searching a BBL library (containing about 150 validated and &#62;50,000 virtual BBLs) with accurately predicted RRVs by support vector regression. The algorithm for hierarchical one-pot synthesis has been implemented in Auto-CHO and uses fragments generated by one-pot reactions as new BBLs. In addition, Auto-CHO allows users to give feedback for virtual BBLs to keep valuable ones for further use. One-pot synthesis of stage-specific embryonic antigen 4 (SSEA-4), which is a pluripotent human embryonic stem cell marker, is demonstrated in this work.

This protocol demonstrates how to use the Auto-CHO software for hierarchical and programmable one-pot synthesis of oligosaccharides. It also describes the general procedure for RRV determination&#160;experiments and one-pot glycosylation of SSEA-4.

Hiyerarşik ve Programlanabilir Tek Pot Oligosakkarit Sentezi

This article presents a general experimental protocol for programmable one-pot oligosaccharide synthesis and demonstrates how to use Auto-CHO software for ...

A Femtoliter Droplet Array for Massively Parallel Protein Synthesis from Single DNA Molecules

Advances in spatial resolution and detection sensitivity of scientific instrumentation make it possible to apply small reactors for biological and chemical research. To meet the demand for high-performance microreactors, we developed a femtoliter droplet array (FemDA) device and exemplified its application in massively parallel cell-free protein synthesis (CFPS) reactions. Over one million uniform droplets were readily generated within a finger-sized area using a two-step oil-sealing protocol. Every droplet was anchored in a femtoliter microchamber composed of a hydrophilic bottom and a hydrophobic sidewall. The hybrid hydrophilic-in-hydrophobic structure and the dedicated sealing oils and surfactants are crucial for stably retaining the femtoliter aqueous solution in the femtoliter space without evaporation loss. The femtoliter configuration and the simple structure of the FemDA device allowed minimal reagent consumption. The uniform dimension of the droplet reactors made large-scale quantitative and time-course measurements convincing and reliable. The FemDA technology correlated the protein yield of the CFPS reaction with the number of DNA molecules in each droplet. We streamlined the procedures about the microfabrication of the device, the formation of the femtoliter droplets, and the acquisition and analysis of the microscopic image data. The detailed protocol with the optimized low running cost makes the FemDA technology accessible to everyone who has standard cleanroom facilities and a conventional fluorescence microscope in their own place.

The overall goal of the protocol is to prepare over one million ordered, uniform, stable, and biocompatible femtoliter droplets on a 1 cm2 planar substrate that can be used for cell-free protein synthesis.