Primary Vinyl Ethers as Acetylene Surrogate: A Flexible Tool for Deuterium‐Labeled Pyrazole Synthesis
A novel synthetic path to 1,3‐disubstituted pyrazoles and their deuterated derivatives was developed. It is based on the reaction of vinyl ethers with hydrazonoyl chlorides in the presence of triethylamine. The reaction mechanism, clarified by the joint experimental and computational study, involves...
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| Veröffentlicht in: | European journal of organic chemistry 2020-08, Vol.2020 (29), p.4571-4580 |
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| container_issue | 29 |
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| container_title | European journal of organic chemistry |
| container_volume | 2020 |
| creator | Ledovskaya, Maria S. Voronin, Vladimir V. Polynski, Mikhail V. Lebedev, Andrey N. Ananikov, Valentine P. |
| description | A novel synthetic path to 1,3‐disubstituted pyrazoles and their deuterated derivatives was developed. It is based on the reaction of vinyl ethers with hydrazonoyl chlorides in the presence of triethylamine. The reaction mechanism, clarified by the joint experimental and computational study, involves 1,3‐dipolar cycloaddition of the in situ generated nitrile imines to vinyl ethers and subsequent cleavage of alcohol from the formed alkoxypyrazoline. The results highlight the possibility of using vinyl ethers as acetylene surrogate and provide a novel access to pyrazoles, 4,5‐dideuteropyrazoles and their regioselectively labeled derivatives, 5‐deuteropyrazoles.
A novel synthetic path to 1,3‐disubstituted pyrazoles, 4,5‐dideuteropyrazoles and 5‐deuteropyrazoles based on the interaction of the readily available vinyl ethers and in situ generated nitrile imines was developed. The joint experimental and computational study clarified the mechanism of the process and allowed us to propose a convenient access to regioselectively deuterated pyrazoles. |
| doi_str_mv | 10.1002/ejoc.202000674 |
| format | Article |
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A novel synthetic path to 1,3‐disubstituted pyrazoles, 4,5‐dideuteropyrazoles and 5‐deuteropyrazoles based on the interaction of the readily available vinyl ethers and in situ generated nitrile imines was developed. The joint experimental and computational study clarified the mechanism of the process and allowed us to propose a convenient access to regioselectively deuterated pyrazoles.</description><identifier>ISSN: 1434-193X</identifier><identifier>EISSN: 1099-0690</identifier><identifier>DOI: 10.1002/ejoc.202000674</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Acetylene ; Cycloaddition ; Derivatives ; Deuteration ; Deuterium ; Deuteropyrazole ; Ethers ; Imines ; Isotopic labeling ; Pyrazole ; Reaction mechanisms ; Triethylamine ; Vinyl ethers</subject><ispartof>European journal of organic chemistry, 2020-08, Vol.2020 (29), p.4571-4580</ispartof><rights>2020 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2020 Wiley‐VCH GmbH</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3834-7b178a44557ae6f649ffceeacb00fd8a6b532e09cf67657ae5f27f5de677fa3</citedby><cites>FETCH-LOGICAL-c3834-7b178a44557ae6f649ffceeacb00fd8a6b532e09cf67657ae5f27f5de677fa3</cites><orcidid>0000-0002-6447-557X</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%2Fejoc.202000674$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fejoc.202000674$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids></links><search><creatorcontrib>Ledovskaya, Maria S.</creatorcontrib><creatorcontrib>Voronin, Vladimir V.</creatorcontrib><creatorcontrib>Polynski, Mikhail V.</creatorcontrib><creatorcontrib>Lebedev, Andrey N.</creatorcontrib><creatorcontrib>Ananikov, Valentine P.</creatorcontrib><title>Primary Vinyl Ethers as Acetylene Surrogate: A Flexible Tool for Deuterium‐Labeled Pyrazole Synthesis</title><title>European journal of organic chemistry</title><description>A novel synthetic path to 1,3‐disubstituted pyrazoles and their deuterated derivatives was developed. It is based on the reaction of vinyl ethers with hydrazonoyl chlorides in the presence of triethylamine. The reaction mechanism, clarified by the joint experimental and computational study, involves 1,3‐dipolar cycloaddition of the in situ generated nitrile imines to vinyl ethers and subsequent cleavage of alcohol from the formed alkoxypyrazoline. The results highlight the possibility of using vinyl ethers as acetylene surrogate and provide a novel access to pyrazoles, 4,5‐dideuteropyrazoles and their regioselectively labeled derivatives, 5‐deuteropyrazoles.
A novel synthetic path to 1,3‐disubstituted pyrazoles, 4,5‐dideuteropyrazoles and 5‐deuteropyrazoles based on the interaction of the readily available vinyl ethers and in situ generated nitrile imines was developed. The joint experimental and computational study clarified the mechanism of the process and allowed us to propose a convenient access to regioselectively deuterated pyrazoles.</description><subject>Acetylene</subject><subject>Cycloaddition</subject><subject>Derivatives</subject><subject>Deuteration</subject><subject>Deuterium</subject><subject>Deuteropyrazole</subject><subject>Ethers</subject><subject>Imines</subject><subject>Isotopic labeling</subject><subject>Pyrazole</subject><subject>Reaction mechanisms</subject><subject>Triethylamine</subject><subject>Vinyl ethers</subject><issn>1434-193X</issn><issn>1099-0690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNqFkL1OwzAURi0EEqWwMltibnESx47ZqtLyo0pFaoXYLCe9LqncuNiJIEw8As_Ik-AqCEame4fzfffqIHQekWFESHwJG1sMYxITQhinB6gXESEGhAlyGHaa0EEkkqdjdOL9JjCCsaiH1g-u3CrX4seyag2e1M_gPFYejwqoWwMV4EXjnF2rGq7wCE8NvJW5Aby01mBtHb6GpgZXNtuvj8-ZysHACj-0Tr3bQC3aKjT60p-iI62Mh7Of2UeL6WQ5vh3M5jd349FsUCRZ-JDnEc8UpWnKFTDNqNC6AFBFToheZYrlaRIDEYVmnO2ZVMdcpytgnGuV9NFF17pz9qUBX8uNbVwVDsqYJkTQTGRZoIYdVTjrvQMtd50EGRG5Vyn3KuWvyhAQXeC1NND-Q8vJ_Xz8l_0Ggpd6mw</recordid><startdate>20200809</startdate><enddate>20200809</enddate><creator>Ledovskaya, Maria S.</creator><creator>Voronin, Vladimir V.</creator><creator>Polynski, Mikhail V.</creator><creator>Lebedev, Andrey N.</creator><creator>Ananikov, Valentine P.</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-6447-557X</orcidid></search><sort><creationdate>20200809</creationdate><title>Primary Vinyl Ethers as Acetylene Surrogate: A Flexible Tool for Deuterium‐Labeled Pyrazole Synthesis</title><author>Ledovskaya, Maria S. ; Voronin, Vladimir V. ; Polynski, Mikhail V. ; Lebedev, Andrey N. ; Ananikov, Valentine P.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3834-7b178a44557ae6f649ffceeacb00fd8a6b532e09cf67657ae5f27f5de677fa3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Acetylene</topic><topic>Cycloaddition</topic><topic>Derivatives</topic><topic>Deuteration</topic><topic>Deuterium</topic><topic>Deuteropyrazole</topic><topic>Ethers</topic><topic>Imines</topic><topic>Isotopic labeling</topic><topic>Pyrazole</topic><topic>Reaction mechanisms</topic><topic>Triethylamine</topic><topic>Vinyl ethers</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ledovskaya, Maria S.</creatorcontrib><creatorcontrib>Voronin, Vladimir V.</creatorcontrib><creatorcontrib>Polynski, Mikhail V.</creatorcontrib><creatorcontrib>Lebedev, Andrey N.</creatorcontrib><creatorcontrib>Ananikov, Valentine P.</creatorcontrib><collection>CrossRef</collection><jtitle>European journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ledovskaya, Maria S.</au><au>Voronin, Vladimir V.</au><au>Polynski, Mikhail V.</au><au>Lebedev, Andrey N.</au><au>Ananikov, Valentine P.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Primary Vinyl Ethers as Acetylene Surrogate: A Flexible Tool for Deuterium‐Labeled Pyrazole Synthesis</atitle><jtitle>European journal of organic chemistry</jtitle><date>2020-08-09</date><risdate>2020</risdate><volume>2020</volume><issue>29</issue><spage>4571</spage><epage>4580</epage><pages>4571-4580</pages><issn>1434-193X</issn><eissn>1099-0690</eissn><abstract>A novel synthetic path to 1,3‐disubstituted pyrazoles and their deuterated derivatives was developed. It is based on the reaction of vinyl ethers with hydrazonoyl chlorides in the presence of triethylamine. The reaction mechanism, clarified by the joint experimental and computational study, involves 1,3‐dipolar cycloaddition of the in situ generated nitrile imines to vinyl ethers and subsequent cleavage of alcohol from the formed alkoxypyrazoline. The results highlight the possibility of using vinyl ethers as acetylene surrogate and provide a novel access to pyrazoles, 4,5‐dideuteropyrazoles and their regioselectively labeled derivatives, 5‐deuteropyrazoles.
A novel synthetic path to 1,3‐disubstituted pyrazoles, 4,5‐dideuteropyrazoles and 5‐deuteropyrazoles based on the interaction of the readily available vinyl ethers and in situ generated nitrile imines was developed. The joint experimental and computational study clarified the mechanism of the process and allowed us to propose a convenient access to regioselectively deuterated pyrazoles.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ejoc.202000674</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0002-6447-557X</orcidid></addata></record> |
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| ispartof | European journal of organic chemistry, 2020-08, Vol.2020 (29), p.4571-4580 |
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| language | eng |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Acetylene Cycloaddition Derivatives Deuteration Deuterium Deuteropyrazole Ethers Imines Isotopic labeling Pyrazole Reaction mechanisms Triethylamine Vinyl ethers |
| title | Primary Vinyl Ethers as Acetylene Surrogate: A Flexible Tool for Deuterium‐Labeled Pyrazole Synthesis |
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