Name: preparation of stable bicyclic aziridinium ions and their ring-opening for the synthesis of azaheterocycles
Uploaded: 2018-08-22T13:30:00
Description: Watch this Scientific Journal Video about Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles at JoVE.com

Dette arbejde blev støttet af den nationale forskning Foundation Korea (NRF-2012M3A7B4049645 og HUFS forskningsfond (2018).

1. Sammenfatning af (6R) -1-[(R)-1-Phenylethyl)-1-Azoniabicyclo [4.1.0] heptan Tosylate (4)
<ol><li>Syntese af 4-(R)-[1-(R) -1-phenylethyl) aziridin-2-yl] butyl 4-methylbenzenesulfonate (2)<ol>
<li>Tilføj 100 mg af 4-[(R)-1-(R)-1-phenylethyl)aziridin-2-yl]butan-1-ol (1)12 (0,46 mmol, 1,0 equiv), 140 µL af triethylamin (Et3N, 1,0 mmol, 2,2 equiv), og en magnetisk stir-bar i en ovn-tørret 25 mL to-hals runde-bunden...

<ol>
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K., Bhattacharyya, A., Das, S., Chauhan, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ring+Expansions+of+Activated+Aziridines+and+Azetidines.">Ring Expansions of Activated Aziridines and Azetidines.</a> Top. Heterocycl. Chem. 41, 49-142 (2016).</li><li>Kim, Y., Ha, H. -. J., Yun, S. Y., Lee, W. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+preparation+of+stable+aziridinium+ions+and+their+ring-openings.">The preparation of stable aziridinium ions and their ring-openings.</a> Chem. Commun. , 4363-4365 (2008).</li><li>D&#8217;hooghe, M., Van Speybroeck, V., Waroquier, M., De Kimpe, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Regio-+and+stereospecific+ring+opening+of+1,1-dialkyl-2-(aryloxymethyl)aziridinium+salts+by+bromide.">Regio- and stereospecific ring opening of 1,1-dialkyl-2-(aryloxymethyl)aziridinium salts by bromide.</a> Chem. Commun. , 1554-1556 (2006).</li><li>Stankovic, S., D'hooghe, M., Catak, S., Eum, H., Waroquier, M., Van Speybroeck, V., De Kimpe, N., Ha, H. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Regioselectivity+in+the+ring+opening+of+non-activated+aziridines.">Regioselectivity in the ring opening of non-activated aziridines.</a> Chem. Soc. Rev. 41, 643-665 (2012).</li><li>Ji, M. K., Hertsen, D., Yoon, D. H., Eum, H., Goossens, H., Waroquier, M., Van Speybroeck, V., D'hooghe, M., De Kimpe, N., Ha, H. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nucleophile-Dependent+Regio-+and+Stereoselective+Ring+Opening+of+1-Azoniabicyclo[3.1.0]hexane+Tosylate.">Nucleophile-Dependent Regio- and Stereoselective Ring Opening of 1-Azoniabicyclo[3.1.0]hexane Tosylate.</a> Chem. Asian J. 9, 1060-1067 (2014).</li><li>Mtro, T. -. X., Duthion, B., Gomez Pardo, D., Cossy, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rearrangement+of+&#946;-amino+alcohols+viaaziridiniums:+a+review.">Rearrangement of &#946;-amino alcohols viaaziridiniums: a review.</a> Chem. Soc. Rev. 39, 89-102 (2010).</li><li>Dolfen, J., Yadav, N. N., De Kimpe, N., D'hooghe, M., Ha, H. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Bicyclic+Aziridinium+Ions+in+Azaheterocyclic+Chemistry-Preparation+and+Synthetic+Application+of+1-Azoniabicyclo[n.1.0]alkanes.">Bicyclic Aziridinium Ions in Azaheterocyclic Chemistry-Preparation and Synthetic Application of 1-Azoniabicyclo[n.1.0]alkanes.</a> Adv. Synth. Catal. 358, 3485-3511 (2016).</li><li>Choi, J., Yadav, N. N., Ha, H. -. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+a+Stable+Bicyclic+Aziridinium+Ion+and+Its+Ring+Expansion+toward+Piperidines+and+Azepanes.">Preparation of a Stable Bicyclic Aziridinium Ion and Its Ring Expansion toward Piperidines and Azepanes.</a> Asian J. Org. Chem. 6, 1292-1307 (2017).</li><li>Yadav, N. N., Choi, J., Ha, H. -. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=One-pot+multiple+reactions:+asymmetric+synthesis+of+2,6-cis-disubstituted+piperidine+alkaloids+from+chiral+aziridine.">One-pot multiple reactions: asymmetric synthesis of 2,6-cis-disubstituted piperidine alkaloids from chiral aziridine.</a> Org. Biomol. Chem. 14, 6426-6434 (2016).</li><li>Angoli, M., Barilli, A., Lesma, G., Passarella, D., Riva, S., Silvani, A., Danieli, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Remote+Stereocenter+Discrimination+in+the+Enzymatic+Resolution+of+Piperidine-2-ethanol.+Short+Enantioselective+Synthesis+of+Sedamine+and+Allosedamine.">Remote Stereocenter Discrimination in the Enzymatic Resolution of Piperidine-2-ethanol. Short Enantioselective Synthesis of Sedamine and Allosedamine.</a> J. Org. Chem. 68, 9525-9527 (2003).</li><li>Shaikh, T. M., Sudalai, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enantioselective+Synthesis+of+(+)-&#945;-Conhydrine+and+(-)-Sedamine+by+L-Proline-Catalysed+&#945;-Aminooxylation.">Enantioselective Synthesis of (+)-&#945;-Conhydrine and (-)-Sedamine by L-Proline-Catalysed &#945;-Aminooxylation.</a> Eur. J. Org. Chem. , 3437-3444 (2010).</li><li>Miyabe, H., Torieda, M., Inoue, K., Tajiri, K., Kiguchi, T., Naito, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Total+Synthesis+of+(&#8722;)-Balanol.">Total Synthesis of (&#8722;)-Balanol.</a> J. Org. Chem. 63, 4397-4407 (1998).</li><li>Castillo, J. A., Calveras, J., Casas, J., Mitjans, M., Vinardell, M. P., Parella, T., Inoue, T., Sprenger, G. 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Piperidin og azepane er to mest udbredte azaheterocycles i mange livreddende medicin og antibiotika, herunder forskellige biologisk aktive naturprodukter16. For at få adgang til både enantiopure Piperidin (5) og azepane (6) med forskellige substituenter, vi develped en effektiv syntetiske metode gennem dannelsen af 1-azoniabicyclo [4.1.0] heptan tosylate fra entiopure 2-(4-hydroxybutyl) aziridne efterfulgt af regiospecific nukleofil angreb på broen eller brohov...

Blandt tre leddede cykliske forbindelser har aziridine lignende ring stamme energi som cyklopropan og oxiran råd til forskellige nitrogen-holdige cyklisk og acycliske forbindelser via ring åbning1,2,3. Dog afhænger karakteristika og reaktivitet af aziridine af erstatningsprodukt ring kvælstof. Aziridine med en tilbagetrækning af elektron gruppe på ring kvælstof4, kaldes "aktiveret aziridine", som er aktiveret til at reagere med den indgående nukleofil uden nogen yderligere aktiverende reagens. På den anden side er "ikke-aktiveret aziridine" med elektron-donere erstatningsprodukt på kvælstof ganske stabil og inert til nukleofiler, medmindre den er aktiveret som en aziridinium ion som jegen (figur 1a)5, 6 , 7. ring åbningen af en ikke-aktiveret aziridine afhænger af forskellige faktorer som substituenter på C2 og C3 kulstof i aziridine, electrophile til at aktivere aziridine ring og den indgående nukleofil. Isolering og karakterisering af en aziridinium ion er ikke mulig på grund af sin høje reaktivitet mod ring-åbning reaktion af nukleofiler, men dets dannelse og egenskaber blev observeret hjælp med en ikke-nukleofil counter anion 5 , 8 , 9 , 10. regio- og stereoselective ring-åbning reaktion af aziridinium ion af en egnet nukleofil udbytter nitrogen-holdige acycliske værdifulde molekyler (P,jeg og Pedersenii)5, 6,7,8,9,10.
En bicykliske aziridinium ion (jegb) genereres på samme måde, eventuelt via fjernelse af forlader gruppen af nukleofil angrebet af ring kvælstof af aziridine i intramolekylære mode (figur 1b). Derefter, denne mellemliggende gennemgår ring-udvidelse med den indgående nukleofil via frigivelse af ring stamme. Dannelse og stabilitet af bicykliske aziridinium ion er afhængig af mange faktorer såsom substituenterne, størrelsen af ring og opløsningsmidler medium9. Regio- og stereoselectivity af aziridine ring-ekspansion er et afgørende aspekt af dens syntetiske nytte, som afhænger af arten af substituenterne i den begyndende substrat og Karakteristik af anvendt nukleofil.
I vores tidlige undersøgelse, lykkedes det os for at forberede 1-azoniabicyclo [3.1.0]hexane tosylate jegb (n = 1) Hvis efterfølgende ring-udvidelse resulterede i dannelsen af en pyrrolidine og en Piperidin (Piii og Piv, n = 1, figur 1)8. Som en del af vores fortsatte undersøgelse på bicykliske aziridinium ion kemi, vi beskriver heri dannelsen af 1-azoniabicyclo [4.1.0]heptane tosylate jegb (n = 2) som et repræsentativt eksempel. Dette blev udarbejdet fra 2-(4-toluensulfonyloxybutyl) aziridine og sin ring-ekspansion blev trigget af en nukleofil råd til værdifulde Piperidin og azepane (P,jeg og Pedersenii, n = 2, figur 1) med forskellige substituenter omkring ring11. Ring-udvidelse af enantiopure aziridine 4-[(R) -1-(R)-1-phenylethyl)aziridin-2-yl]butan-1-ol (1) resulterede i asymmetriske syntesen af substituerede azaheterocycles, der gælder for bygge biologisk aktive molekyler med Piperidin og azepane skelet. Denne syntetiske protokol er blevet anvendt til forskellige forbindelser spænder fra enkle 2-cyanomethylpiperidine 5f, 2-acetyloxymethylpiperidine 5 h og 3-hydroxyazepane 6j til mere komplekse molekyler herunder naturlige produkter såsom fagomine (9), febrifugine analog (12) og balanol (15) i optisk ren former11.

<table border="0" cellpadding="0" cellspacing="0" width="1213">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Thin Layer Chromatography (TLC)</td>
			<td style="width:260px;">Merck</td>
			<td style="width:207px;">100390</td>
			<td style="width:183px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">UV light</td>
			<td style="width:260px;">Sigma-Aldrich</td>
			<td>Z169625-1EA</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">Bruker AVANCE III HD (400 MHz) spectrometer</td>
			<td style="width:260px;">Bruker</td>
			<td style="width:207px;">NA</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">JASCO P-2000</td>
			<td style="width:260px;">JASCO</td>
			<td style="width:207px;">P-2000</td>
			<td>For optical rotation</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">High resolution mass spectra/ MALDI-TOF/TOF Mass Spectrometry</td>
			<td style="width:260px;">AB SCIEX</td>
			<td style="width:207px;">4800 Plus&#160;</td>
			<td>High resolution mass spectra</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">(2R)-1-[(1R)-1-Phenylethyl]-2-aziridinecarboxylic acid (&#8211;)-menthol ester, 98%</td>
			<td style="width:260px;">Sigma-Aldrich</td>
			<td style="width:207px;">57,054-0</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">(2S)-1-[(1R)-1-Phenylethyl]-2-aziridinecarboxylic acid (&#8211;)-menthol ester</td>
			<td style="width:260px;">Sigma-Aldrich</td>
			<td style="width:207px;">57,051-6</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Triethylethylamine</td>
			<td style="width:260px;">DAEJUNG</td>
			<td style="width:207px;">8556-4400-1L</td>
			<td>CAS No: 121-44-8</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Dichloromethane</td>
			<td style="width:260px;">SAMCHUN</td>
			<td style="width:207px;">M0822-18L</td>
			<td>CAS No: 75-09-2</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">p-Toluenesulfonic anhydride</td>
			<td style="width:260px;">Sigma-Aldrich</td>
			<td style="width:207px;">259764-25G</td>
			<td>CAS No: 4124-41-8</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">n-Hexane</td>
			<td style="width:260px;">SAMCHUN</td>
			<td style="width:207px;">H0114-18L</td>
			<td>CAS No: 110-54-3</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Ethyl acetate</td>
			<td style="width:260px;">SAMCHUN</td>
			<td style="width:207px;">E0191-18L</td>
			<td>CAS No: 141-78-6</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Sodium sulfate</td>
			<td style="width:260px;">SAMCHUN</td>
			<td style="width:207px;">S1011-1kg</td>
			<td>CAS No: 7757-82-6</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Acetonitrile-d3</td>
			<td style="width:260px;">Cambridge Isotope Laboratories, Inc</td>
			<td style="width:207px;">15G-744-25g</td>
			<td>CAS No: 2206-26-0</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Acetonitrile</td>
			<td style="width:260px;">SAMCHUN</td>
			<td style="width:207px;">A0127-18L</td>
			<td>CAS No: 75-05-8</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">1,4-Dioxane</td>
			<td style="width:260px;">SAMCHUN</td>
			<td style="width:207px;">D0654-1kg</td>
			<td>CAS No: 123-91-1</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Sodium hydroxide</td>
			<td style="width:260px;">DUKSAN</td>
			<td style="width:207px;">A31226-1kg</td>
			<td>CAS No: 1310-73-2</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Sodium acetate</td>
			<td style="width:260px;">Alfa Aesar</td>
			<td style="width:207px;">11554-250g</td>
			<td>CAS No: 127-09-3</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Lithium aluminum hydride</td>
			<td style="width:260px;">TCI</td>
			<td style="width:207px;">L0203-100g</td>
			<td>CAS No: 16853-85-3</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Tetrahydrofuran</td>
			<td style="width:260px;">SAMCHUN</td>
			<td style="width:207px;">T0148-18L</td>
			<td>CAS No: 109-99-9</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Sodium azide</td>
			<td style="width:260px;">D.S.P</td>
			<td style="width:207px;">703301-500g</td>
			<td>CAS No: 26628-22-8</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Cesium fluoride</td>
			<td style="width:260px;">aldrich</td>
			<td style="width:207px;">18951-0250-25g</td>
			<td>CAS No: 13400-13-0</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Tetrabutylammonium bromide</td>
			<td style="width:260px;">aldrich</td>
			<td style="width:207px;">426288-25g</td>
			<td>CAS No: 1643-19-2</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Sodium iodide</td>
			<td style="width:260px;">aldrich</td>
			<td style="width:207px;">383112-100g</td>
			<td>CAS No: 7681-82-5</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Sodium cyanide</td>
			<td style="width:260px;">Acros Organics</td>
			<td style="width:207px;">424301000-100g</td>
			<td>CAS No: 143-33-9</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Sodium thiocyanate</td>
			<td style="width:260px;">aldrich</td>
			<td style="width:207px;">467871-250g</td>
			<td>CAS No: 540-72-7</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Sodium methoxide</td>
			<td style="width:260px;">aldrich</td>
			<td style="width:207px;">156256-1L</td>
			<td>CAS No: 124-41-4</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Benzylamine</td>
			<td style="width:260px;">Alfa Aesar</td>
			<td style="width:207px;">A10997-1000g</td>
			<td>CAS No: 100-46-9</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Phenol</td>
			<td style="width:260px;">TCI</td>
			<td style="width:207px;">P1610-500g</td>
			<td>CAS No: 108-95-2</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Sodium benzoate</td>
			<td style="width:260px;">Alfa Aesar</td>
			<td style="width:207px;">A15946-250g</td>
			<td>CAS No: 532-32-1</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:564px;">Chloroform-d</td>
			<td style="width:260px;">Cambridge Isotope Laboratories, Inc</td>
			<td style="width:207px;">DLM-7TB-100S/16H-239, 100g</td>
			<td>CAS No: 865-49-6</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Dimethyl sulfoxide-d6</td>
			<td style="width:260px;">Cambridge Isotope Laboratories, Inc</td>
			<td style="width:207px;">DLM-10-25, 25g</td>
			<td>CAS No: 2206-27-1</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Methanol</td>
			<td style="width:260px;">SAMCHUN</td>
			<td style="width:207px;">M0585-18L</td>
			<td>CAS No: 67-56-1</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:564px;">Ninhydrin</td>
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preparation of stable bicyclic aziridinium ions and their ring-opening for the synthesis of azaheterocycles

Bicykliske aziridinium ioner blev genereret ved fjernelse af en passende forlader gruppen gennem interne nukleofil angreb af nitrogen atom i aziridine ring. Nytten af bicykliske aziridinium ioner, specielt 1-azoniabicyclo [3.1.0] hexan og 1-azoniabicyclo [4.1.0] heptan tosylate fremhævet i aziridine ring åbninger af nukleofil med udgivelsen af ring stammen at udbytte de tilsvarende ring-udvidet azaheterocycles som pyrrolidine, Piperidin og azepane med forskellige substituenter på ringen i regio- og stereospecific måde. Heri, rapporterer vi en enkel og bekvem metode til forberedelse af den stabile 1-azabicyclo [4.1.0] heptan tosylate efterfulgt af selektiv ring åbne via en nukleofil angreb på broen eller brohoved carbon at udbytte Piperidin og azepane ringe, henholdsvis. Denne syntetiske strategi tillod os at forberede biologisk aktive naturlige produkter indeholdende Piperidin og azepane motiv, herunder sedamine, allosedamine, fagomine og balanol på særdeles effektiv måde.

Reaktionen af 4-[(R) -1-(R)-1-phenylethyl)aziridin-2-yl]butan-1-ol (1)12 med p- toluenesulfonic eddikesyreanhydrid og triethylamin i CH2Cl2 ved stuetemperatur til 1,0 h givet den tilsvarende 2 - udbytte (4-tosyloxybutyl) aziridine 2 i 96%11. 1 H NMR (400 MHz) spektrum af sammensatte 2 CD3CN på forskellige tidsintervaller...

Watch this Scientific Journal Video about Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles at JoVE.com

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles

Forberedelse af stabile bicykliske Aziridinium ioner og deres Ring-åbning for syntese af Azaheterocycles

Bicykliske aziridinium ioner som 1-azoniabicyclo [4.1.0] heptan tosylate blev genereret fra 2-[4-tolenesulfonyloxybutyl] aziridine, som blev udnyttet til fremstilling af substituerede piperidines og azepanes via regio- og stereospecific ring-udvidelse med forskellige nukleofiler. Denne højeffektive protokol tillod os at forberede forskellige azaheterocycles herunder naturlige produkter som fagomine, febrifugine analog og balanol.

Bicyclic aziridinium ions were generated by the removal of an appropriate leaving group through internal nucleophilic attack by nitrogen atom in the ...

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Nucleophilic Substitution and Elimination Reactions of Alkyl Halides

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