Reversed steric order of reactivity for tert‐butyl and adamantyl‐3‐cyanomethylene‐1,2,4‐triazines
Reactions of 2‐(6‐tert‐butyl‐5‐oxo‐4,5‐dihydro‐1,2,4‐triazin‐3(2H)‐ylidene)‐3‐oxo‐3‐R‐propanenitriles (R = t‐Bu, Ad‐1) with tert‐butyl bromoacetate gave the corresponding N(2), C(5)O bis‐alkylation products. Treatment of the latter with t‐BuLi, in the case of R = t‐Bu, led to intramolecular condens...
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Veröffentlicht in: | Journal of heterocyclic chemistry 2021-06, Vol.58 (6), p.1371-1378 |
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container_title | Journal of heterocyclic chemistry |
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creator | Ivanov, Sergey M. |
description | Reactions of 2‐(6‐tert‐butyl‐5‐oxo‐4,5‐dihydro‐1,2,4‐triazin‐3(2H)‐ylidene)‐3‐oxo‐3‐R‐propanenitriles (R = t‐Bu, Ad‐1) with tert‐butyl bromoacetate gave the corresponding N(2), C(5)O bis‐alkylation products. Treatment of the latter with t‐BuLi, in the case of R = t‐Bu, led to intramolecular condensation at the exocyclic nitrile group. However, in the case of R = Ad‐1, the condensation with the sterically more hindered carbonyl group was observed to give diastereomerically pure 8‐cyanopyrrolo[1,2‐b][1,2,4]triazine‐6‐carboxylate derivatives. The structures of the isolated products were confirmed by spectral methods and X‐ray single‐crystal diffraction. |
doi_str_mv | 10.1002/jhet.4255 |
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Treatment of the latter with t‐BuLi, in the case of R = t‐Bu, led to intramolecular condensation at the exocyclic nitrile group. However, in the case of R = Ad‐1, the condensation with the sterically more hindered carbonyl group was observed to give diastereomerically pure 8‐cyanopyrrolo[1,2‐b][1,2,4]triazine‐6‐carboxylate derivatives. The structures of the isolated products were confirmed by spectral methods and X‐ray single‐crystal diffraction.</description><identifier>ISSN: 0022-152X</identifier><identifier>EISSN: 1943-5193</identifier><identifier>DOI: 10.1002/jhet.4255</identifier><language>eng</language><publisher>Chichester, UK: John Wiley & Sons, Inc</publisher><subject>Alkylation ; Carbonyl groups ; Carbonyls ; Condensates ; Spectral methods</subject><ispartof>Journal of heterocyclic chemistry, 2021-06, Vol.58 (6), p.1371-1378</ispartof><rights>2021 Wiley Periodicals LLC.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c2975-2988e15e6ae91e368055a3ba4576a5978269f01cea6247bb56a87a04151573183</citedby><cites>FETCH-LOGICAL-c2975-2988e15e6ae91e368055a3ba4576a5978269f01cea6247bb56a87a04151573183</cites><orcidid>0000-0003-1233-4430</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fjhet.4255$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fjhet.4255$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids></links><search><creatorcontrib>Ivanov, Sergey M.</creatorcontrib><title>Reversed steric order of reactivity for tert‐butyl and adamantyl‐3‐cyanomethylene‐1,2,4‐triazines</title><title>Journal of heterocyclic chemistry</title><description>Reactions of 2‐(6‐tert‐butyl‐5‐oxo‐4,5‐dihydro‐1,2,4‐triazin‐3(2H)‐ylidene)‐3‐oxo‐3‐R‐propanenitriles (R = t‐Bu, Ad‐1) with tert‐butyl bromoacetate gave the corresponding N(2), C(5)O bis‐alkylation products. Treatment of the latter with t‐BuLi, in the case of R = t‐Bu, led to intramolecular condensation at the exocyclic nitrile group. However, in the case of R = Ad‐1, the condensation with the sterically more hindered carbonyl group was observed to give diastereomerically pure 8‐cyanopyrrolo[1,2‐b][1,2,4]triazine‐6‐carboxylate derivatives. The structures of the isolated products were confirmed by spectral methods and X‐ray single‐crystal diffraction.</description><subject>Alkylation</subject><subject>Carbonyl groups</subject><subject>Carbonyls</subject><subject>Condensates</subject><subject>Spectral methods</subject><issn>0022-152X</issn><issn>1943-5193</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNp1UM1Kw0AQXkTBWj34BguehKbN7mayyVFKtUpBkArewiSZ0NQ2qbvbSjz5CD6jT-LWepVhGL6fmYGPsUsRDkUYytFyQW4YSYAj1hNppAIQqTpmPa_JQIB8OWVn1i49FErrHnt9oh0ZSyW3jkxd8NaUZHhbcUNYuHpXu45XreFedd-fX_nWdSuOTcmxxDU2HnlW-S46bNo1uUW3ooY8IQZyEPnpTI0fdUP2nJ1UuLJ08Tf77Pl2Mh9Pg9nj3f34ZhYUMtUQyDRJSADFSKkgFSchAKocI9AxQqoTGadVKArCWEY6zyHGRGMYCRCglUhUn10d7m5M-7Yl67JluzWNf5lJUACxinz12fXBVZjWWkNVtjH1Gk2XiTDbZ5nts8z2WXrv6OB9r1fU_W_MHqaT-e_GD1Mzesk</recordid><startdate>202106</startdate><enddate>202106</enddate><creator>Ivanov, Sergey M.</creator><general>John Wiley & Sons, Inc</general><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0003-1233-4430</orcidid></search><sort><creationdate>202106</creationdate><title>Reversed steric order of reactivity for tert‐butyl and adamantyl‐3‐cyanomethylene‐1,2,4‐triazines</title><author>Ivanov, Sergey M.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2975-2988e15e6ae91e368055a3ba4576a5978269f01cea6247bb56a87a04151573183</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Alkylation</topic><topic>Carbonyl groups</topic><topic>Carbonyls</topic><topic>Condensates</topic><topic>Spectral methods</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ivanov, Sergey M.</creatorcontrib><collection>CrossRef</collection><jtitle>Journal of heterocyclic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ivanov, Sergey M.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reversed steric order of reactivity for tert‐butyl and adamantyl‐3‐cyanomethylene‐1,2,4‐triazines</atitle><jtitle>Journal of heterocyclic chemistry</jtitle><date>2021-06</date><risdate>2021</risdate><volume>58</volume><issue>6</issue><spage>1371</spage><epage>1378</epage><pages>1371-1378</pages><issn>0022-152X</issn><eissn>1943-5193</eissn><abstract>Reactions of 2‐(6‐tert‐butyl‐5‐oxo‐4,5‐dihydro‐1,2,4‐triazin‐3(2H)‐ylidene)‐3‐oxo‐3‐R‐propanenitriles (R = t‐Bu, Ad‐1) with tert‐butyl bromoacetate gave the corresponding N(2), C(5)O bis‐alkylation products. Treatment of the latter with t‐BuLi, in the case of R = t‐Bu, led to intramolecular condensation at the exocyclic nitrile group. However, in the case of R = Ad‐1, the condensation with the sterically more hindered carbonyl group was observed to give diastereomerically pure 8‐cyanopyrrolo[1,2‐b][1,2,4]triazine‐6‐carboxylate derivatives. The structures of the isolated products were confirmed by spectral methods and X‐ray single‐crystal diffraction.</abstract><cop>Chichester, UK</cop><pub>John Wiley & Sons, Inc</pub><doi>10.1002/jhet.4255</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0003-1233-4430</orcidid></addata></record> |
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subjects | Alkylation Carbonyl groups Carbonyls Condensates Spectral methods |
title | Reversed steric order of reactivity for tert‐butyl and adamantyl‐3‐cyanomethylene‐1,2,4‐triazines |
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