Not‐So‐Innocent Anions Determine the Mechanism of Cationic Alkylators
Alkylating reagents based on thioimidazolium ionic liquids were synthesized and the influence of the anion on the alkylation reaction mechanism explored in detail using both experimental and computational methods. Thioimidazolium cations transfer alkyl substituents to nucleophiles, however the react...
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| Veröffentlicht in: | Chemistry : a European journal 2021-02, Vol.27 (10), p.3440-3448 |
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| creator | Taimoory, S. Maryamdokht Cataldo, Vincenzo Alessandro Schäfer, Andreas Trant, John F. Guterman, Ryan |
| description | Alkylating reagents based on thioimidazolium ionic liquids were synthesized and the influence of the anion on the alkylation reaction mechanism explored in detail using both experimental and computational methods. Thioimidazolium cations transfer alkyl substituents to nucleophiles, however the reaction rate was highly dependent on anion identity, demonstrating that the anion is not innocent in the mechanism. Detailed analysis of the computationally‐derived potential energy surfaces associated with possible mechanisms indicated that this dependence arises from a combination of anion induced electronic, steric and coordinating effects, with highly nucleophilic anions catalyzing a 2‐step process while highly non‐nucleophilic, delocalized anions favor a 1‐step reaction. This work also confirms the presence of ion‐pairs and aggregates in solution thus supporting anion‐induced control over the reaction rate and mechanism. These findings provide new insight into an old reaction allowing for better design of cationic alkylators in synthesis, gene expression, polymer science, and protein chemistry applications.
Alkylating reagents based on thioimidazolium ionic liquids were synthesized and the influence of the anion on the alkylation reaction mechanism explored in detail using both experimental and computational methods. |
| doi_str_mv | 10.1002/chem.202004208 |
| format | Article |
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Alkylating reagents based on thioimidazolium ionic liquids were synthesized and the influence of the anion on the alkylation reaction mechanism explored in detail using both experimental and computational methods.</description><subject>Alkylation</subject><subject>Anions</subject><subject>Cations</subject><subject>Chemical synthesis</subject><subject>Chemistry</subject><subject>colloids</subject><subject>computational chemistry</subject><subject>Computer applications</subject><subject>Gene expression</subject><subject>Ionic liquids</subject><subject>Ions</subject><subject>Nucleophiles</subject><subject>Polymers</subject><subject>Potential energy</subject><subject>Reaction mechanisms</subject><subject>Reagents</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFkb1uFDEURi0EIkugpUQj0dDMcv039jRIqyWQlRIogNryOndYhxk72LOJtuMReEaeBI82bAgNjV3cc4_up4-Q5xTmFIC9dhsc5gwYgGCgH5AZlYzWXDXyIZlBK1TdSN4ekSc5XwJA23D-mBxxTrliQszI6kMcf_34-SmWZxVCdBjGahF8DLl6iyOmwQesxg1W5-g2Nvg8VLGrlnYsiHfVov-26-0YU35KHnW2z_js9j8mX96dfF6e1mcf36-Wi7PaSZC6RrqWjnFqddeIruNOcyvwYq00E9h0ACWWdaxzWnAKEhWCs-jKDLUWivJj8mbvvdquB7yYDk62N1fJDzbtTLTe3J8EvzFf47VRutWqnQSvbgUpft9iHs3gs8O-twHjNhsmpGKaUjmhL_9BL-M2hRKvULqlElrFCzXfUy7FnBN2h2MomKklM7VkDi2VhRd_Rzjgf2opQLsHbnyPu__ozPL05PxO_hvwYqCZ</recordid><startdate>20210215</startdate><enddate>20210215</enddate><creator>Taimoory, S. 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Maryamdokht</creatorcontrib><creatorcontrib>Cataldo, Vincenzo Alessandro</creatorcontrib><creatorcontrib>Schäfer, Andreas</creatorcontrib><creatorcontrib>Trant, John F.</creatorcontrib><creatorcontrib>Guterman, Ryan</creatorcontrib><collection>Wiley Online Library Open Access</collection><collection>Wiley Online Library (Open Access Collection)</collection><collection>PubMed</collection><collection>CrossRef</collection><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><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Taimoory, S. 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Detailed analysis of the computationally‐derived potential energy surfaces associated with possible mechanisms indicated that this dependence arises from a combination of anion induced electronic, steric and coordinating effects, with highly nucleophilic anions catalyzing a 2‐step process while highly non‐nucleophilic, delocalized anions favor a 1‐step reaction. This work also confirms the presence of ion‐pairs and aggregates in solution thus supporting anion‐induced control over the reaction rate and mechanism. These findings provide new insight into an old reaction allowing for better design of cationic alkylators in synthesis, gene expression, polymer science, and protein chemistry applications.
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| subjects | Alkylation Anions Cations Chemical synthesis Chemistry colloids computational chemistry Computer applications Gene expression Ionic liquids Ions Nucleophiles Polymers Potential energy Reaction mechanisms Reagents |
| title | Not‐So‐Innocent Anions Determine the Mechanism of Cationic Alkylators |
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