N‐Aryl and N‐Alkyl Carbamates from 1 Atmosphere of CO2
We have successfully isolated and characterized the zinc carbamate complex (phen)Zn(OAc)(OC(=O)NHPh) (1; phen=1,10‐phenanthroline), formed as an intermediate during the Zn(OAc)2/phen‐catalyzed synthesis of organic carbamates from CO2, amines, and the reusable reactant Si(OMe)4. Density functional th...
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Veröffentlicht in: | Chemistry : a European journal 2021-12, Vol.27 (72), p.18066-18073 |
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creator | Takeuchi, Katsuhiko Chen, Ming‐Yu Yuan, Hao‐Yu Koizumi, Hiroki Matsumoto, Kazuhiro Fukaya, Norihisa Choe, Yoong‐Kee Shigeyasu, Shinji Matsumoto, Seiji Hamura, Satoshi Choi, Jun‐Chul |
description | We have successfully isolated and characterized the zinc carbamate complex (phen)Zn(OAc)(OC(=O)NHPh) (1; phen=1,10‐phenanthroline), formed as an intermediate during the Zn(OAc)2/phen‐catalyzed synthesis of organic carbamates from CO2, amines, and the reusable reactant Si(OMe)4. Density functional theory calculations revealed that the direct reaction of 1 with Si(OMe)4 proceeds via a five‐coordinate silicon intermediate, forming organic carbamates. Based on these results, the catalytic system was improved by using Si(OMe)4 as the reaction solvent and additives like KOMe and KF, which promote the formation of the five‐coordinated silicon species. This sustainable and effective method can be used to synthesize various N‐aryl and N‐alkyl carbamates, including industrially important polyurethane raw materials, starting from CO2 under atmospheric pressure.
We have isolated and analyzed the reactivity of the key intermediate 1 formed during the Zn(OAc)2/phen‐catalyzed synthesis of organic carbamates starting from amines, CO2, and Si(OMe)4. The reaction mechanism was analyzed by using DFT. The catalytic system was modified and various N‐aryl and N‐alkyl carbamates that could be used as industrially important polyurethane raw materials were synthesized by using atmospheric CO2. |
doi_str_mv | 10.1002/chem.202103587 |
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We have isolated and analyzed the reactivity of the key intermediate 1 formed during the Zn(OAc)2/phen‐catalyzed synthesis of organic carbamates starting from amines, CO2, and Si(OMe)4. The reaction mechanism was analyzed by using DFT. The catalytic system was modified and various N‐aryl and N‐alkyl carbamates that could be used as industrially important polyurethane raw materials were synthesized by using atmospheric CO2.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.202103587</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Additives ; Amines ; Aromatic compounds ; Carbamates (tradename) ; Carbon dioxide ; carbon dioxide fixation ; Chemical synthesis ; Chemistry ; density functional calculations ; Density functional theory ; Polyurethane ; Polyurethane resins ; Raw materials ; Silicon ; sustainable chemistry ; Zinc</subject><ispartof>Chemistry : a European journal, 2021-12, Vol.27 (72), p.18066-18073</ispartof><rights>2021 Wiley‐VCH GmbH</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><orcidid>0000-0002-2720-5394 ; 0000-0001-8319-803X ; 0000-0003-1580-8822 ; 0000-0002-7049-5032 ; 0000-0002-9061-3761</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%2Fchem.202103587$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.202103587$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids></links><search><creatorcontrib>Takeuchi, Katsuhiko</creatorcontrib><creatorcontrib>Chen, Ming‐Yu</creatorcontrib><creatorcontrib>Yuan, Hao‐Yu</creatorcontrib><creatorcontrib>Koizumi, Hiroki</creatorcontrib><creatorcontrib>Matsumoto, Kazuhiro</creatorcontrib><creatorcontrib>Fukaya, Norihisa</creatorcontrib><creatorcontrib>Choe, Yoong‐Kee</creatorcontrib><creatorcontrib>Shigeyasu, Shinji</creatorcontrib><creatorcontrib>Matsumoto, Seiji</creatorcontrib><creatorcontrib>Hamura, Satoshi</creatorcontrib><creatorcontrib>Choi, Jun‐Chul</creatorcontrib><title>N‐Aryl and N‐Alkyl Carbamates from 1 Atmosphere of CO2</title><title>Chemistry : a European journal</title><description>We have successfully isolated and characterized the zinc carbamate complex (phen)Zn(OAc)(OC(=O)NHPh) (1; phen=1,10‐phenanthroline), formed as an intermediate during the Zn(OAc)2/phen‐catalyzed synthesis of organic carbamates from CO2, amines, and the reusable reactant Si(OMe)4. Density functional theory calculations revealed that the direct reaction of 1 with Si(OMe)4 proceeds via a five‐coordinate silicon intermediate, forming organic carbamates. Based on these results, the catalytic system was improved by using Si(OMe)4 as the reaction solvent and additives like KOMe and KF, which promote the formation of the five‐coordinated silicon species. This sustainable and effective method can be used to synthesize various N‐aryl and N‐alkyl carbamates, including industrially important polyurethane raw materials, starting from CO2 under atmospheric pressure.
We have isolated and analyzed the reactivity of the key intermediate 1 formed during the Zn(OAc)2/phen‐catalyzed synthesis of organic carbamates starting from amines, CO2, and Si(OMe)4. The reaction mechanism was analyzed by using DFT. The catalytic system was modified and various N‐aryl and N‐alkyl carbamates that could be used as industrially important polyurethane raw materials were synthesized by using atmospheric CO2.</description><subject>Additives</subject><subject>Amines</subject><subject>Aromatic compounds</subject><subject>Carbamates (tradename)</subject><subject>Carbon dioxide</subject><subject>carbon dioxide fixation</subject><subject>Chemical synthesis</subject><subject>Chemistry</subject><subject>density functional calculations</subject><subject>Density functional theory</subject><subject>Polyurethane</subject><subject>Polyurethane resins</subject><subject>Raw materials</subject><subject>Silicon</subject><subject>sustainable chemistry</subject><subject>Zinc</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNpdkL1OAzEQhC0EEiHQUp9EQ3NhvZvzD110Cj9SgAZqy-fYSsJdLtiJUDoegWfkSbgASoG2WH2a0WpnGDvnMOAAeOVmvhkgIAcqlDxgPV4gz0mK4pD1QA9lLgrSx-wkpQUAaEHUY9ePXx-fo7itM7ucZj9Qv3ZU2ljZxq59ykJsm4xno3XTptXMR5-1ISuf8JQdBVsnf_a3--zlZvxc3uWTp9v7cjTJF0QocxeCIuIVFqpSQdDQoXAgSVpweuolKAFodQjYyY4q0BoF7bRq6CpN1GeXv3dXsX3b-LQ2zTw5X9d26dtNMlhoqUAVXe4-u_hnXbSbuOy-Myi6URJRdi7963qf135rVnHe2Lg1HMyuR7Pr0ex7NOXd-GFP9A0qWWeg</recordid><startdate>20211223</startdate><enddate>20211223</enddate><creator>Takeuchi, Katsuhiko</creator><creator>Chen, Ming‐Yu</creator><creator>Yuan, Hao‐Yu</creator><creator>Koizumi, Hiroki</creator><creator>Matsumoto, Kazuhiro</creator><creator>Fukaya, Norihisa</creator><creator>Choe, Yoong‐Kee</creator><creator>Shigeyasu, Shinji</creator><creator>Matsumoto, Seiji</creator><creator>Hamura, Satoshi</creator><creator>Choi, Jun‐Chul</creator><general>Wiley Subscription Services, Inc</general><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-2720-5394</orcidid><orcidid>https://orcid.org/0000-0001-8319-803X</orcidid><orcidid>https://orcid.org/0000-0003-1580-8822</orcidid><orcidid>https://orcid.org/0000-0002-7049-5032</orcidid><orcidid>https://orcid.org/0000-0002-9061-3761</orcidid></search><sort><creationdate>20211223</creationdate><title>N‐Aryl and N‐Alkyl Carbamates from 1 Atmosphere of CO2</title><author>Takeuchi, Katsuhiko ; Chen, Ming‐Yu ; Yuan, Hao‐Yu ; Koizumi, Hiroki ; Matsumoto, Kazuhiro ; Fukaya, Norihisa ; Choe, Yoong‐Kee ; Shigeyasu, Shinji ; Matsumoto, Seiji ; Hamura, Satoshi ; Choi, Jun‐Chul</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-j3327-cff8331b258b8f634c26c0737a0c9de708602a9ff2b8fc3b0992630c9db4cb933</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Additives</topic><topic>Amines</topic><topic>Aromatic compounds</topic><topic>Carbamates (tradename)</topic><topic>Carbon dioxide</topic><topic>carbon dioxide fixation</topic><topic>Chemical synthesis</topic><topic>Chemistry</topic><topic>density functional calculations</topic><topic>Density functional theory</topic><topic>Polyurethane</topic><topic>Polyurethane resins</topic><topic>Raw materials</topic><topic>Silicon</topic><topic>sustainable chemistry</topic><topic>Zinc</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Takeuchi, Katsuhiko</creatorcontrib><creatorcontrib>Chen, Ming‐Yu</creatorcontrib><creatorcontrib>Yuan, Hao‐Yu</creatorcontrib><creatorcontrib>Koizumi, Hiroki</creatorcontrib><creatorcontrib>Matsumoto, Kazuhiro</creatorcontrib><creatorcontrib>Fukaya, Norihisa</creatorcontrib><creatorcontrib>Choe, Yoong‐Kee</creatorcontrib><creatorcontrib>Shigeyasu, Shinji</creatorcontrib><creatorcontrib>Matsumoto, Seiji</creatorcontrib><creatorcontrib>Hamura, Satoshi</creatorcontrib><creatorcontrib>Choi, Jun‐Chul</creatorcontrib><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Takeuchi, Katsuhiko</au><au>Chen, Ming‐Yu</au><au>Yuan, Hao‐Yu</au><au>Koizumi, Hiroki</au><au>Matsumoto, Kazuhiro</au><au>Fukaya, Norihisa</au><au>Choe, Yoong‐Kee</au><au>Shigeyasu, Shinji</au><au>Matsumoto, Seiji</au><au>Hamura, Satoshi</au><au>Choi, Jun‐Chul</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>N‐Aryl and N‐Alkyl Carbamates from 1 Atmosphere of CO2</atitle><jtitle>Chemistry : a European journal</jtitle><date>2021-12-23</date><risdate>2021</risdate><volume>27</volume><issue>72</issue><spage>18066</spage><epage>18073</epage><pages>18066-18073</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>We have successfully isolated and characterized the zinc carbamate complex (phen)Zn(OAc)(OC(=O)NHPh) (1; phen=1,10‐phenanthroline), formed as an intermediate during the Zn(OAc)2/phen‐catalyzed synthesis of organic carbamates from CO2, amines, and the reusable reactant Si(OMe)4. Density functional theory calculations revealed that the direct reaction of 1 with Si(OMe)4 proceeds via a five‐coordinate silicon intermediate, forming organic carbamates. Based on these results, the catalytic system was improved by using Si(OMe)4 as the reaction solvent and additives like KOMe and KF, which promote the formation of the five‐coordinated silicon species. This sustainable and effective method can be used to synthesize various N‐aryl and N‐alkyl carbamates, including industrially important polyurethane raw materials, starting from CO2 under atmospheric pressure.
We have isolated and analyzed the reactivity of the key intermediate 1 formed during the Zn(OAc)2/phen‐catalyzed synthesis of organic carbamates starting from amines, CO2, and Si(OMe)4. The reaction mechanism was analyzed by using DFT. The catalytic system was modified and various N‐aryl and N‐alkyl carbamates that could be used as industrially important polyurethane raw materials were synthesized by using atmospheric CO2.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/chem.202103587</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-2720-5394</orcidid><orcidid>https://orcid.org/0000-0001-8319-803X</orcidid><orcidid>https://orcid.org/0000-0003-1580-8822</orcidid><orcidid>https://orcid.org/0000-0002-7049-5032</orcidid><orcidid>https://orcid.org/0000-0002-9061-3761</orcidid></addata></record> |
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subjects | Additives Amines Aromatic compounds Carbamates (tradename) Carbon dioxide carbon dioxide fixation Chemical synthesis Chemistry density functional calculations Density functional theory Polyurethane Polyurethane resins Raw materials Silicon sustainable chemistry Zinc |
title | N‐Aryl and N‐Alkyl Carbamates from 1 Atmosphere of CO2 |
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