Contact ion-pair SN2 reactions activated by Lewis Base Phase transfer catalysts
Abstract We present experimental probes of contact ion-pair (CIP) SN2 reactions for simplest prototype systems by 19F-NMR spectroscopy. This study provides crucial evidences for the reactions of CIP metal salts facilitated by Lewis base phase transfer catalysts (PTCs) [2,2,2]-cryptand, 18-crown-6, p...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-55795-6 |
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| author | Ju Gyeong Jeong Young-Ho Oh Tae Hyun Park Sung-Sik Lee Dong Wook Kim Sungyul Lee |
| author_facet | Ju Gyeong Jeong Young-Ho Oh Tae Hyun Park Sung-Sik Lee Dong Wook Kim Sungyul Lee |
| author_sort | Ju Gyeong Jeong |
| collection | DOAJ |
| description | Abstract We present experimental probes of contact ion-pair (CIP) SN2 reactions for simplest prototype systems by 19F-NMR spectroscopy. This study provides crucial evidences for the reactions of CIP metal salts facilitated by Lewis base phase transfer catalysts (PTCs) [2,2,2]-cryptand, 18-crown-6, pentaethylene glycols (pentaEGs) and BINOL–based pentaEG. The 19F-NMR spectra of MF (M = K, Cs) ion-pairs in various solvents are used as fingerprinting tools to identify the CIP CsF/PTC/substrate complexes in SN2 reactions. Examination of the prototype reactions demonstrates that the novel CIP mechanism, which is in sharp contrast to the conventional perspectives, may account for the observed phenomenal efficiency of the SN2 processes using the alkali metal salts under the influence of various PTCs. In this extremely efficient and selective protocol of wide applicability, the CIP MF is activated by the Lewis base PTCs acting on the counter-cation M+ to drastically mitigate the latter’s retarding Coulomb forces on the adjacent nucleophile F-, with or without the participation of hydrogen bonds. |
| format | Article |
| id | doaj-art-795df3f22e334484918980a1160d51e9 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-795df3f22e334484918980a1160d51e92025-02-02T12:33:16ZengNature PortfolioNature Communications2041-17232025-01-0116111110.1038/s41467-024-55795-6Contact ion-pair SN2 reactions activated by Lewis Base Phase transfer catalystsJu Gyeong Jeong0Young-Ho Oh1Tae Hyun Park2Sung-Sik Lee3Dong Wook Kim4Sungyul Lee5Department of Chemistry, Inha University, 100 Inha-ro, Nam-guDepartment of Applied Chemistry, Kyung Hee University, Yongin CityDepartment of Chemistry, Inha University, 100 Inha-ro, Nam-guDepartment of Applied Chemistry, Kyung Hee University, Yongin CityDepartment of Chemistry, Inha University, 100 Inha-ro, Nam-guDepartment of Applied Chemistry, Kyung Hee University, Yongin CityAbstract We present experimental probes of contact ion-pair (CIP) SN2 reactions for simplest prototype systems by 19F-NMR spectroscopy. This study provides crucial evidences for the reactions of CIP metal salts facilitated by Lewis base phase transfer catalysts (PTCs) [2,2,2]-cryptand, 18-crown-6, pentaethylene glycols (pentaEGs) and BINOL–based pentaEG. The 19F-NMR spectra of MF (M = K, Cs) ion-pairs in various solvents are used as fingerprinting tools to identify the CIP CsF/PTC/substrate complexes in SN2 reactions. Examination of the prototype reactions demonstrates that the novel CIP mechanism, which is in sharp contrast to the conventional perspectives, may account for the observed phenomenal efficiency of the SN2 processes using the alkali metal salts under the influence of various PTCs. In this extremely efficient and selective protocol of wide applicability, the CIP MF is activated by the Lewis base PTCs acting on the counter-cation M+ to drastically mitigate the latter’s retarding Coulomb forces on the adjacent nucleophile F-, with or without the participation of hydrogen bonds.https://doi.org/10.1038/s41467-024-55795-6 |
| spellingShingle | Ju Gyeong Jeong Young-Ho Oh Tae Hyun Park Sung-Sik Lee Dong Wook Kim Sungyul Lee Contact ion-pair SN2 reactions activated by Lewis Base Phase transfer catalysts Nature Communications |
| title | Contact ion-pair SN2 reactions activated by Lewis Base Phase transfer catalysts |
| title_full | Contact ion-pair SN2 reactions activated by Lewis Base Phase transfer catalysts |
| title_fullStr | Contact ion-pair SN2 reactions activated by Lewis Base Phase transfer catalysts |
| title_full_unstemmed | Contact ion-pair SN2 reactions activated by Lewis Base Phase transfer catalysts |
| title_short | Contact ion-pair SN2 reactions activated by Lewis Base Phase transfer catalysts |
| title_sort | contact ion pair sn2 reactions activated by lewis base phase transfer catalysts |
| url | https://doi.org/10.1038/s41467-024-55795-6 |
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