4-Amino-TEMPO as N-Nucleophile in Palladium-Catalyzed Aminocarbonylation

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• 作者：Má ; té ; Gergely ; Attila Taká ; cs and Lá ; szl&oacute ; Kollá ; r
• 刊名：Journal of Heterocyclic Chemistry
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：54
• 期：1
• 页码：634-640
• 全文大小：508K
• ISSN：1943-5193

文摘

Palladium-catalyzed n class="TH_term4">aminocarbonylationn> of lns:w="http://www.wiley.com/namespaces/wiley" xmlns:cr="urn://wiley-online-library/content/render" xmlns:mml="http://www.w3.org/1998/Math/MathML" id="jhet2635-eo-0001">n class="TH_term1 TH_term3">iodobenzenen> and iodoalkenes (lns:w="http://www.wiley.com/namespaces/wiley" xmlns:cr="urn://wiley-online-library/content/render" xmlns:mml="http://www.w3.org/1998/Math/MathML" id="jhet2635-eo-0006">n class="TH_term3">1-iodocyclohexenen>, lns:w="http://www.wiley.com/namespaces/wiley" xmlns:cr="urn://wiley-online-library/content/render" xmlns:mml="http://www.w3.org/1998/Math/MathML" id="jhet2635-eo-0009">n class="TH_term3">4-tert-butyl-1-iodocyclohexenen>, lns:w="http://www.wiley.com/namespaces/wiley" xmlns:cr="urn://wiley-online-library/content/render" xmlns:mml="http://www.w3.org/1998/Math/MathML" id="jhet2635-eo-0012">n class="TH_term3">α-iodostyrenen>, 17-iodoandrost-16-ene) was carried out using a free radical (4-amino-TEMPO) for the first time. Its reduced form (lns:w="http://www.wiley.com/namespaces/wiley" xmlns:cr="urn://wiley-online-library/content/render" xmlns:mml="http://www.w3.org/1998/Math/MathML" id="jhet2635-eo-0019">n class="TH_term3">4-amino-2,2,6,6-tetramethylpiperidinen>) was also used as N-nucleophile. The free radical was partially reduced under n class="TH_term4">aminocarbonylationn> conditions; however, the isolation of carbonylated products bearing a stable radical moiety was successfully accomplished. It was proved that the reduction of the 1-oxyl functionality took place to higher extent when more severe conditions (40 bar CO pressure) were used. The mixture of carboxamide and 2-ketocarboxamide products was obtained using n class="TH_term1 TH_term3">iodobenzenen> because of single and double n class="TH_term6">carbon monoxiden> insertion, respectively. In turn, carboxamide derivatives were formed exclusively when iodoalkenes were used as substrates.