A mild and readily scalable procedure for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate and its applications to the N-difluoromethylation of indazole, benzotriazole, imidazole, indole and pyrazole derivatives
[Display omitted] •Mild condition.•Scalable.•Suitable for substartes bearing labile groups. A set of mild conditions for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate (1) with chlorodifluoromethane (CHClF2) on large scale (up to 33 g) is described. A...
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| Veröffentlicht in: | Journal of fluorine chemistry 2020-06, Vol.234, p.109514, Article 109514 |
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| container_title | Journal of fluorine chemistry |
| container_volume | 234 |
| creator | Hong, Zhenqiu Hou, Xiaoping Zhao, Rulin Li, Jianqing Pawluczyk, Joseph Wang, Bei Kempson, James Khandelwal, Purnima Smith, Leon M. Glunz, Peter Mathur, Arvind |
| description | [Display omitted]
•Mild condition.•Scalable.•Suitable for substartes bearing labile groups.
A set of mild conditions for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate (1) with chlorodifluoromethane (CHClF2) on large scale (up to 33 g) is described. An optimized N-1-difluoromethylation of the functionalized indazole 1 was achieved, under an atmosphere of CHClF2 (balloon) in the presence of NaH and catalytic amounts of NaI and 18-crown-6 ether at a moderate temperature (40 °C). This procedure provides a safe and convenient alternative to existing approaches that require high pressures and/or the use of NaH in DMF at high temperatures that would present a safety concern when operating on a large scale. This method was extended to the N-difluoromethylation of indazole, benzotriazole, imidazole, indole and pyrazole derivatives, all of which bear an ester group. |
| doi_str_mv | 10.1016/j.jfluchem.2020.109514 |
| format | Article |
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•Mild condition.•Scalable.•Suitable for substartes bearing labile groups.
A set of mild conditions for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate (1) with chlorodifluoromethane (CHClF2) on large scale (up to 33 g) is described. An optimized N-1-difluoromethylation of the functionalized indazole 1 was achieved, under an atmosphere of CHClF2 (balloon) in the presence of NaH and catalytic amounts of NaI and 18-crown-6 ether at a moderate temperature (40 °C). This procedure provides a safe and convenient alternative to existing approaches that require high pressures and/or the use of NaH in DMF at high temperatures that would present a safety concern when operating on a large scale. This method was extended to the N-difluoromethylation of indazole, benzotriazole, imidazole, indole and pyrazole derivatives, all of which bear an ester group.</description><identifier>ISSN: 0022-1139</identifier><identifier>EISSN: 1873-3328</identifier><identifier>DOI: 10.1016/j.jfluchem.2020.109514</identifier><language>eng</language><publisher>Lausanne: Elsevier B.V</publisher><subject>18-crown-6 ether ; Benzotriazole ; Chlorodifluoromethane ; Derivatives ; High temperature ; Imidazole ; Indazole ; Indoles ; N-1-difluoromethylation ; NaI ; Pyrazole</subject><ispartof>Journal of fluorine chemistry, 2020-06, Vol.234, p.109514, Article 109514</ispartof><rights>2020 Elsevier B.V.</rights><rights>Copyright Elsevier BV Jun 2020</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c340t-e4c391ae69b32e00cd10cadfbbd5efcd772ff6cc557be2b6dc9fd780c807728f3</citedby><cites>FETCH-LOGICAL-c340t-e4c391ae69b32e00cd10cadfbbd5efcd772ff6cc557be2b6dc9fd780c807728f3</cites><orcidid>0000-0002-7702-4006</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://dx.doi.org/10.1016/j.jfluchem.2020.109514$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>314,780,784,3550,27924,27925,45995</link.rule.ids></links><search><creatorcontrib>Hong, Zhenqiu</creatorcontrib><creatorcontrib>Hou, Xiaoping</creatorcontrib><creatorcontrib>Zhao, Rulin</creatorcontrib><creatorcontrib>Li, Jianqing</creatorcontrib><creatorcontrib>Pawluczyk, Joseph</creatorcontrib><creatorcontrib>Wang, Bei</creatorcontrib><creatorcontrib>Kempson, James</creatorcontrib><creatorcontrib>Khandelwal, Purnima</creatorcontrib><creatorcontrib>Smith, Leon M.</creatorcontrib><creatorcontrib>Glunz, Peter</creatorcontrib><creatorcontrib>Mathur, Arvind</creatorcontrib><title>A mild and readily scalable procedure for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate and its applications to the N-difluoromethylation of indazole, benzotriazole, imidazole, indole and pyrazole derivatives</title><title>Journal of fluorine chemistry</title><description>[Display omitted]
•Mild condition.•Scalable.•Suitable for substartes bearing labile groups.
A set of mild conditions for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate (1) with chlorodifluoromethane (CHClF2) on large scale (up to 33 g) is described. An optimized N-1-difluoromethylation of the functionalized indazole 1 was achieved, under an atmosphere of CHClF2 (balloon) in the presence of NaH and catalytic amounts of NaI and 18-crown-6 ether at a moderate temperature (40 °C). This procedure provides a safe and convenient alternative to existing approaches that require high pressures and/or the use of NaH in DMF at high temperatures that would present a safety concern when operating on a large scale. This method was extended to the N-difluoromethylation of indazole, benzotriazole, imidazole, indole and pyrazole derivatives, all of which bear an ester group.</description><subject>18-crown-6 ether</subject><subject>Benzotriazole</subject><subject>Chlorodifluoromethane</subject><subject>Derivatives</subject><subject>High temperature</subject><subject>Imidazole</subject><subject>Indazole</subject><subject>Indoles</subject><subject>N-1-difluoromethylation</subject><subject>NaI</subject><subject>Pyrazole</subject><issn>0022-1139</issn><issn>1873-3328</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNqFkctu1DAUhkNVJIbCKyBLbFoJD7Zz31FVLa1UwQbWlmMfaxw5cbCdUdOnx5OZWSJWR-f2_cf-s-wTJVtKaPW13_baznIHw5YRdii2JS0usg1t6hznOWsusw0hjGFK8_Zd9j6EnhBSk7rZvLm4RYOxColRIQ9CGbugIIUVnQU0eSdBzR6Qdh7FHaAfmGJlkpzzboC4W6yIxo3IabRmqMLX1xF8xN0cF6vMtINxsSFh7Y17WW4wfcRmVOLVWcA5lsJ3qZwosJ5gYkBimqyRKzeg6E66_1A9s76gDsZXF705pWYw506aSXHlT4tfi0iBN_tE2UP4kL3Vwgb4eIpX2e-H-193j_j55_enu9tnLPOCRAyFzFsqoGq7nAEhUlEihdJdp0rQUtU107qSsizrDlhXKdlqVTdENiS1Gp1fZZ-P3PStf2YIkfdu9mOS5KwoKtZWTVmmqeo4Jb0LwYPmkzeD8AunhB_85j0_-80PfvOj32nx23ER0hv2BjwP0sCYDDQeZOTKmf8h_gLG3b7u</recordid><startdate>202006</startdate><enddate>202006</enddate><creator>Hong, Zhenqiu</creator><creator>Hou, Xiaoping</creator><creator>Zhao, Rulin</creator><creator>Li, Jianqing</creator><creator>Pawluczyk, Joseph</creator><creator>Wang, Bei</creator><creator>Kempson, James</creator><creator>Khandelwal, Purnima</creator><creator>Smith, Leon M.</creator><creator>Glunz, Peter</creator><creator>Mathur, Arvind</creator><general>Elsevier B.V</general><general>Elsevier BV</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7QF</scope><scope>7QO</scope><scope>7QP</scope><scope>7QQ</scope><scope>7SC</scope><scope>7SE</scope><scope>7SP</scope><scope>7SR</scope><scope>7TA</scope><scope>7TB</scope><scope>7U5</scope><scope>7U7</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>F28</scope><scope>FR3</scope><scope>H8D</scope><scope>H8G</scope><scope>JG9</scope><scope>JQ2</scope><scope>KR7</scope><scope>L7M</scope><scope>L~C</scope><scope>L~D</scope><scope>P64</scope><orcidid>https://orcid.org/0000-0002-7702-4006</orcidid></search><sort><creationdate>202006</creationdate><title>A mild and readily scalable procedure for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate and its applications to the N-difluoromethylation of indazole, benzotriazole, imidazole, indole and pyrazole derivatives</title><author>Hong, Zhenqiu ; Hou, Xiaoping ; Zhao, Rulin ; Li, Jianqing ; Pawluczyk, Joseph ; Wang, Bei ; Kempson, James ; Khandelwal, Purnima ; Smith, Leon M. ; Glunz, Peter ; Mathur, Arvind</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c340t-e4c391ae69b32e00cd10cadfbbd5efcd772ff6cc557be2b6dc9fd780c807728f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>18-crown-6 ether</topic><topic>Benzotriazole</topic><topic>Chlorodifluoromethane</topic><topic>Derivatives</topic><topic>High temperature</topic><topic>Imidazole</topic><topic>Indazole</topic><topic>Indoles</topic><topic>N-1-difluoromethylation</topic><topic>NaI</topic><topic>Pyrazole</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hong, Zhenqiu</creatorcontrib><creatorcontrib>Hou, Xiaoping</creatorcontrib><creatorcontrib>Zhao, Rulin</creatorcontrib><creatorcontrib>Li, Jianqing</creatorcontrib><creatorcontrib>Pawluczyk, Joseph</creatorcontrib><creatorcontrib>Wang, Bei</creatorcontrib><creatorcontrib>Kempson, James</creatorcontrib><creatorcontrib>Khandelwal, Purnima</creatorcontrib><creatorcontrib>Smith, Leon M.</creatorcontrib><creatorcontrib>Glunz, Peter</creatorcontrib><creatorcontrib>Mathur, Arvind</creatorcontrib><collection>CrossRef</collection><collection>Aluminium Industry Abstracts</collection><collection>Biotechnology Research Abstracts</collection><collection>Calcium & Calcified Tissue Abstracts</collection><collection>Ceramic Abstracts</collection><collection>Computer and Information Systems Abstracts</collection><collection>Corrosion Abstracts</collection><collection>Electronics & Communications Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Materials Business File</collection><collection>Mechanical & Transportation Engineering Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Toxicology Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>ANTE: Abstracts in New Technology & Engineering</collection><collection>Engineering Research Database</collection><collection>Aerospace Database</collection><collection>Copper Technical Reference Library</collection><collection>Materials Research Database</collection><collection>ProQuest Computer Science Collection</collection><collection>Civil Engineering Abstracts</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Computer and Information Systems Abstracts Academic</collection><collection>Computer and Information Systems Abstracts Professional</collection><collection>Biotechnology and BioEngineering Abstracts</collection><jtitle>Journal of fluorine chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hong, Zhenqiu</au><au>Hou, Xiaoping</au><au>Zhao, Rulin</au><au>Li, Jianqing</au><au>Pawluczyk, Joseph</au><au>Wang, Bei</au><au>Kempson, James</au><au>Khandelwal, Purnima</au><au>Smith, Leon M.</au><au>Glunz, Peter</au><au>Mathur, Arvind</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A mild and readily scalable procedure for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate and its applications to the N-difluoromethylation of indazole, benzotriazole, imidazole, indole and pyrazole derivatives</atitle><jtitle>Journal of fluorine chemistry</jtitle><date>2020-06</date><risdate>2020</risdate><volume>234</volume><spage>109514</spage><pages>109514-</pages><artnum>109514</artnum><issn>0022-1139</issn><eissn>1873-3328</eissn><abstract>[Display omitted]
•Mild condition.•Scalable.•Suitable for substartes bearing labile groups.
A set of mild conditions for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate (1) with chlorodifluoromethane (CHClF2) on large scale (up to 33 g) is described. An optimized N-1-difluoromethylation of the functionalized indazole 1 was achieved, under an atmosphere of CHClF2 (balloon) in the presence of NaH and catalytic amounts of NaI and 18-crown-6 ether at a moderate temperature (40 °C). This procedure provides a safe and convenient alternative to existing approaches that require high pressures and/or the use of NaH in DMF at high temperatures that would present a safety concern when operating on a large scale. This method was extended to the N-difluoromethylation of indazole, benzotriazole, imidazole, indole and pyrazole derivatives, all of which bear an ester group.</abstract><cop>Lausanne</cop><pub>Elsevier B.V</pub><doi>10.1016/j.jfluchem.2020.109514</doi><orcidid>https://orcid.org/0000-0002-7702-4006</orcidid></addata></record> |
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| ispartof | Journal of fluorine chemistry, 2020-06, Vol.234, p.109514, Article 109514 |
| issn | 0022-1139 1873-3328 |
| language | eng |
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| source | Elsevier ScienceDirect Journals Complete |
| subjects | 18-crown-6 ether Benzotriazole Chlorodifluoromethane Derivatives High temperature Imidazole Indazole Indoles N-1-difluoromethylation NaI Pyrazole |
| title | A mild and readily scalable procedure for the N-1-difluoromethylation of ethyl 6-((tert-butyldiphenylsilyl)oxy)-1H-indazole-3-carboxylate and its applications to the N-difluoromethylation of indazole, benzotriazole, imidazole, indole and pyrazole derivatives |
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