Unveiling the mechanism of N‐methylation of indole with dimethylcarbonate using either DABCO or DBU as catalyst
Depending on the catalyst used, N‐methylation of indole with dimethylcarbonate (DMC)—an environmentally friendly alkylation agent—yields different products. With 1,4‐diazabicyclo[2.2.2]octane (DABCO), the reaction forms only N‐methylated indole, but with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU), bot...
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| Veröffentlicht in: | Journal of mass spectrometry. 2021-03, Vol.56 (3), p.e4707-n/a |
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| container_title | Journal of mass spectrometry. |
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| creator | Vendramini, Pedro H. Zeoly, Lucas A. Cormanich, Rodrigo A. Buehl, Michael Eberlin, Marcos N. Ferreira, Bruno R.V. |
| description | Depending on the catalyst used, N‐methylation of indole with dimethylcarbonate (DMC)—an environmentally friendly alkylation agent—yields different products. With 1,4‐diazabicyclo[2.2.2]octane (DABCO), the reaction forms only N‐methylated indole, but with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU), both N‐methylated and N‐methoxycarbonylated indole are formed. Using direct ESI(+)‐MS monitoring to collect actual snapshots of the changing ionic composition of the reaction solution, we report on the interception and characterization of key intermediates for such reactions. Although a mechanism has been proposed with methoxycarbonylated base as the key intermediate for both DBU and DABCO, the ESI(+)‐MS data and B3LYP‐D3/6‐311+G** calculations suggest that the reaction of DMC with indole under either DABCO or DBU catalysis follows contrasting mechanisms. |
| doi_str_mv | 10.1002/jms.4707 |
| format | Article |
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With 1,4‐diazabicyclo[2.2.2]octane (DABCO), the reaction forms only N‐methylated indole, but with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU), both N‐methylated and N‐methoxycarbonylated indole are formed. Using direct ESI(+)‐MS monitoring to collect actual snapshots of the changing ionic composition of the reaction solution, we report on the interception and characterization of key intermediates for such reactions. Although a mechanism has been proposed with methoxycarbonylated base as the key intermediate for both DBU and DABCO, the ESI(+)‐MS data and B3LYP‐D3/6‐311+G** calculations suggest that the reaction of DMC with indole under either DABCO or DBU catalysis follows contrasting mechanisms.</description><identifier>ISSN: 1076-5174</identifier><identifier>EISSN: 1096-9888</identifier><identifier>DOI: 10.1002/jms.4707</identifier><identifier>PMID: 33590578</identifier><language>eng</language><publisher>England: Wiley Subscription Services, Inc</publisher><subject>Alkylation ; Catalysis ; Catalysts ; density functional theory calculations ; ESI(+)‐MS/MS ; indole ; Indoles ; Interception ; Intermediates ; mechanism ; Methylation ; N‐methylation</subject><ispartof>Journal of mass spectrometry., 2021-03, Vol.56 (3), p.e4707-n/a</ispartof><rights>2021 John Wiley & Sons, Ltd.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4207-4cfe92620b46c3e5057e45111f0566ad43638566dc5031283de842d2763694673</citedby><cites>FETCH-LOGICAL-c4207-4cfe92620b46c3e5057e45111f0566ad43638566dc5031283de842d2763694673</cites><orcidid>0000-0003-4716-4080 ; 0000-0001-7584-2139 ; 0000-0001-9653-7248</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%2Fjms.4707$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fjms.4707$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/33590578$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Vendramini, Pedro H.</creatorcontrib><creatorcontrib>Zeoly, Lucas A.</creatorcontrib><creatorcontrib>Cormanich, Rodrigo A.</creatorcontrib><creatorcontrib>Buehl, Michael</creatorcontrib><creatorcontrib>Eberlin, Marcos N.</creatorcontrib><creatorcontrib>Ferreira, Bruno R.V.</creatorcontrib><title>Unveiling the mechanism of N‐methylation of indole with dimethylcarbonate using either DABCO or DBU as catalyst</title><title>Journal of mass spectrometry.</title><addtitle>J Mass Spectrom</addtitle><description>Depending on the catalyst used, N‐methylation of indole with dimethylcarbonate (DMC)—an environmentally friendly alkylation agent—yields different products. 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| subjects | Alkylation Catalysis Catalysts density functional theory calculations ESI(+)‐MS/MS indole Indoles Interception Intermediates mechanism Methylation N‐methylation |
| title | Unveiling the mechanism of N‐methylation of indole with dimethylcarbonate using either DABCO or DBU as catalyst |
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