Name: one-pot microwave-assisted conversion of anomeric nitrate-esters to trichloroacetimidates
Uploaded: 2018-01-15T13:00:00
Description: Watch this Scientific Journal Video about One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates at JoVE.com

Forfatterne vil gerne anerkende Vanderbilt University og kemiske Biologisk Institut for økonomisk støtte. Mr. Berkley Ellis og Prof. John McLean er anerkendt for High-Resolution masse spektralanalyse.

1. repræsentant mikrobølgeovn-assisteret Denitration
<ol><li>Placer azido nitrat ester (1,0-ækvivalent, 0,2 mmol) i en 8 mL mikrobølgeovn prøveglas. Omfanget af reaktionen kan øges til flere mmol uden nogen negativ virkning på reaktion fremskridt.</li>
	<li>Opløse azido-nitrat ester i 20% aq. acetone (0,1 M, 2,0 mL). Tilføje pyridin (5.0-ækvivalent, 0,08 mL, 1,0 mmol) til reaktion fartøj. Cap mikrobølgeovn bestråling hætteglas og placere reaktion fartøj i en mikrobølgeovn reaktor hulrum.</li>
	<li>Bestr...

<ol>
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E., Ottosson, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Armed-Disarmed+Effects+in+Glycosyl+Donors+-+Rationalization+and+Sidetracking.">Armed-Disarmed Effects in Glycosyl Donors - Rationalization and Sidetracking.</a> J. Org. Chem. 55 (25), 6068-6070 (1990).</li><li>Bohe, L., Crich, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+propos+of+glycosyl+cations+and+the+mechanism+of+chemical+glycosylation;+the+current+state+of+the+art.">A propos of glycosyl cations and the mechanism of chemical glycosylation; the current state of the art.</a> Carbohydr. Res. 403, 48-59 (2015).</li><li>Toshima, K., Tatsuta, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Recent+Progress+in+O-Glycosylation+Methods+and+Its+Application+to+Natural-Products+Synthesis.">Recent Progress in O-Glycosylation Methods and Its Application to Natural-Products Synthesis.</a> Chem. Rev. 93 (4), 1503-1531 (1993).</li><li>Koenigs, W., Knorr, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ueber+einige+Derivate+des+Traubenzuckers+und+der+Galactose.">Ueber einige Derivate des Traubenzuckers und der Galactose.</a> Chem. 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History and recent advances.</a> Carbohydrate Research. 344 (9), 1110-1122 (2009).</li><li>Lian, G., Zhang, X., Yu, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thioglycosides+in+carbohydrate+research.">Thioglycosides in carbohydrate research.</a> Carbohydr. Res. 403, 13-22 (2015).</li><li>Schmidt, R. R., Kinzy, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Anomeric-Oxygen+Activation+for+Glycoside+Synthesis+-+the+Trichloroacetimidate+Method.">Anomeric-Oxygen Activation for Glycoside Synthesis - the Trichloroacetimidate Method.</a> Advances in Carbohydrate Chemistry and Biochemistry. 50, 21-123 (1994).</li><li>Schmidt, R. R., Toepfer, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Glycosylation+with+highly+reactive+glycosyl+donors:+efficiency+of+the+inverse+procedure.">Glycosylation with highly reactive glycosyl donors: efficiency of the inverse procedure.</a> Tetrahedron Lett. 32 (28), 3353-3356 (1991).</li><li>Keith, D. J., Townsend, S. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct,+microwave-assisted+substitution+of+anomeric+nitrate-esters.">Direct, microwave-assisted substitution of anomeric nitrate-esters.</a> Carbohydr. 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Den protokol, der er beskrevet i dette selvstudium indeholder en metode til at konvertere nitrat estere til nyttige, reaktiv funktionalitet. I en bredere forstand har ansætte en mikrobølgeovn reaktor til at fuldføre særlige manøvrer i løbet af en kulhydrat syntese potentiale til at gøre vanskeligt transformationer letkøbt og rutine. Vores mål med denne tutorial er at vise, hvordan man håndterer kulhydrater i forbindelse med mikrobølgeovn bestråling.
I forbindelse med den overordned...

Som følge af deres allestedsnærværelse i Molekylærbiologi, har kulhydrater været langvarige mål for kemisk syntese. 1 , 2 , 3 kernen i enhver vellykket syntetiske kampagne er den korrekte installation af glykosylering reaktioner at bygge oligosaccharid kæde. 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 ikke overraskende, der er et stort antal af metoder til at installere glykosidbindinger. 13 , 14 den Koenigs-Knorr metode er en af de tidligste kendte procedurer og involverer kobling en glycosyl chlorid eller bromid med en alkoholiske komponent, normalt under tungmetaller (kviksølv eller sølv) aktivering. 15 relaterede glycosyl fluorider blev først introduceret som donorer i 1981 af gruppen Mukaiyama og har fundet udbredt anvendelse på grund af deres øget termisk og kemisk stabilitet. 16 på den modsatte ende af reaktivitet spektrum er glycosyl jodider, som er langt mere reaktiv end de øvrige halogenider. Øget reaktivitet er ledsaget af øget stereocontrol, især når danner α-linked oligosaccharider. 17 ud over "haloglycosides", thioglycosides har fundet bred nytte, delvis på grund af deres lethed af dannelse, stabilitet til et væld af reaktionsbetingelser og aktivering med elektrofil reagenser. 18
Metoderne beskrevet ovenfor fokus på konvertering af en anomere alkohol til en "ikke-ilt" indeholdende, latent forlader gruppe, der er aktiveret og i sidste ende fordrevet af en alkohol fra en acceptor molekyle. Anomere ilt aktivering fokuserer som beskrevet af Schmidt skole, på konvertering C1 ilt, sig selv, at en forlader gruppen. 19 denne metode er den mest kraftfulde og udbredt meget i kemiske glykosylering reaktioner. Trichloroacetimidate donorer er let tilberedt af en reducerende sukker og trichloroacetonitrile i en base som kaliumcarbonat (K2CO3) eller 1,8-diazabicyclo [5.4.0] undec-7-en (DBU). Disse arter er derefter aktiveres ved hjælp af Lewis syrer. 20
Vi har for nylig rapporteret, at 2-azido-1-trichloroacetimidate donorer kan tilberedes direkte fra glycals. Processen indebærer en to reaktion, en-pot procedure fra 2-azido-1-nitrat estere. 21 denne detaljerede protokollen er beregnet til at hjælpe praktiserende læger i endt transformation i højt udbytte. Af særlig interesse er det første trin i den rækkefølge, der fokuserer på termisk denitration under mikrobølgeovn - assisteret varme. Vi håber også at give en visuel tutorial på beskæftiger mikrobølgeovn reaktorer i organisk syntese.

<table>
	<tbody>
		<tr>
			<td>230 400 mesh silica gel</td>
			<td>SiliCycle Inc</td>
			<td>R10030B</td>
			<td></td>
		</tr>
		<tr>
			<td>TLC plates</td>
			<td>SiliCycle Inc</td>
			<td>TLG-R10014B-527</td>
			<td></td>
		</tr>
		<tr>
			<td>Ceric ammonium molybdate</td>
			<td>Sigma-Aldrich</td>
			<td>A1343</td>
			<td></td>
		</tr>
		<tr>
			<td>Solvent Still</td>
			<td>Mbraun</td>
			<td>MB-SPS-800</td>
			<td></td>
		</tr>
		<tr>
			<td>Infared spectrometer</td>
			<td>Thermo</td>
			<td>Thermo Electron IR100</td>
			<td></td>
		</tr>
		<tr>
			<td>Nuclear Magnetic Resonance</td>
			<td>Bruker</td>
			<td></td>
			<td>400, 600 MHz</td>
		</tr>
		<tr>
			<td>LC/MS</td>
			<td>Thermo/Dionex</td>
			<td></td>
			<td>Single quad, ESI</td>
		</tr>
		<tr>
			<td>HRMS</td>
			<td>Agilent</td>
			<td>Synapt G2 S HDMS</td>
			<td></td>
		</tr>
		<tr>
			<td>Microwave reactor</td>
			<td>Anton Parr</td>
			<td>Anton Parr G10 Monowave 200</td>
			<td></td>
		</tr>
		<tr>
			<td>DBU</td>
			<td>Sigma-Aldrich</td>
			<td>139009</td>
			<td></td>
		</tr>
		<tr>
			<td>CCl3CN</td>
			<td>Sigma-Aldrich</td>
			<td>T53805</td>
			<td></td>
		</tr>
		<tr>
			<td>Pyridine</td>
			<td>Sigma-Aldrich</td>
			<td>270970</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetone</td>
			<td>Fisher Scientific</td>
			<td>A18-20</td>
			<td>Tech. grade</td>
		</tr>
		<tr>
			<td>Phase separator</td>
			<td>Biotage</td>
			<td>120-1901-A</td>
			<td></td>
		</tr>
		<tr>
			<td>Rotary evaporator</td>
			<td>Buchi</td>
			<td>R-100</td>
			<td></td>
		</tr>
	</tbody>
</table>

one-pot microwave-assisted conversion of anomeric nitrate-esters to trichloroacetimidates

Målet med den følgende fremgangsmåde er at give en demonstration af en-pot konvertering af en 2-azido-1-nitrat-ester til en trichloroacetimidate glycosyl donor. Efter azido-nitrering af en glycal, kan produktet 2-azido-1-nitrat ester hydrolyseret under mikrobølgeovn-assisteret bestråling. Denne transformation er normalt opnås ved hjælp af stærkt nukleofil reagenser og udvidede reaktionstider. Mikrobølgeovn bestråling inducerer hydrolyse, i mangel af reagenser, med korte reaktionstider. Efter denitration omdannes den mellemliggende anomere alkohol i den samme gryde, til de tilsvarende 2-azido-1-trichloroacetimidate.

Den teknologi, der er beskrevet heri blev demonstreret på en pulje af tre 2-azido-1-nitrat estere. I hvert tilfælde var det første trin i reaktionen komplet inden for 20 minutter.
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56610/56610fig2v3.jpg"> Figur 2. Repræsentativt eksempel hydrolyse (1 ->2), og en-pot konvertering af 2-azido-1-nitrat ester af <strong...

Watch this Scientific Journal Video about One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates at JoVE.com

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

One-pot mikrobølgeovn-assisteret konvertering af anomere nitrat-estere til Trichloroacetimidates

En 2-azido-1-nitrat-ester kan konverteres til den tilsvarende 2-azido-1-trichloroacetimidate i et en-pot procedure. Målet med håndskriftet er at påvise nytten af mikrobølgeovn reaktoren i kulhydrat syntese.

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 ...

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