Conformational preferences of α-fluoroketones may influence their reactivity
Fluorine has been shown in many cases to impart specific and predictable effects on molecular conformation. Here it is shown that these conformational effects may have an influence on reactivity through studying the relative reactivity of various α-halogenated ketones towards borohydride reduction....
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2017-12-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.13.284 |
| _version_ | 1819275202979168256 |
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| author | Graham Pattison |
| author_facet | Graham Pattison |
| author_sort | Graham Pattison |
| collection | DOAJ |
| description | Fluorine has been shown in many cases to impart specific and predictable effects on molecular conformation. Here it is shown that these conformational effects may have an influence on reactivity through studying the relative reactivity of various α-halogenated ketones towards borohydride reduction. These results demonstrate that the α-fluoro ketones are in fact a little less reactive than the corresponding α-chloro and α-bromo derivatives. It is suggested, supported by computation, that this effect is due to reactive conformations in which the C–X bond is orthogonal to the carbonyl group for good orbital overlap being disfavoured in the case of fluoro ketones. |
| first_indexed | 2024-12-23T23:20:35Z |
| format | Article |
| id | doaj.art-dccd057eed9c4cd2905976398adb99fb |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-23T23:20:35Z |
| publishDate | 2017-12-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-dccd057eed9c4cd2905976398adb99fb2022-12-21T17:26:22ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972017-12-011312915292110.3762/bjoc.13.2841860-5397-13-284Conformational preferences of α-fluoroketones may influence their reactivityGraham Pattison0Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, UKFluorine has been shown in many cases to impart specific and predictable effects on molecular conformation. Here it is shown that these conformational effects may have an influence on reactivity through studying the relative reactivity of various α-halogenated ketones towards borohydride reduction. These results demonstrate that the α-fluoro ketones are in fact a little less reactive than the corresponding α-chloro and α-bromo derivatives. It is suggested, supported by computation, that this effect is due to reactive conformations in which the C–X bond is orthogonal to the carbonyl group for good orbital overlap being disfavoured in the case of fluoro ketones.https://doi.org/10.3762/bjoc.13.284α-halogenated ketonesconformational analysisreactivitystereoelectronic effects |
| spellingShingle | Graham Pattison Conformational preferences of α-fluoroketones may influence their reactivity Beilstein Journal of Organic Chemistry α-halogenated ketones conformational analysis reactivity stereoelectronic effects |
| title | Conformational preferences of α-fluoroketones may influence their reactivity |
| title_full | Conformational preferences of α-fluoroketones may influence their reactivity |
| title_fullStr | Conformational preferences of α-fluoroketones may influence their reactivity |
| title_full_unstemmed | Conformational preferences of α-fluoroketones may influence their reactivity |
| title_short | Conformational preferences of α-fluoroketones may influence their reactivity |
| title_sort | conformational preferences of α fluoroketones may influence their reactivity |
| topic | α-halogenated ketones conformational analysis reactivity stereoelectronic effects |
| url | https://doi.org/10.3762/bjoc.13.284 |
| work_keys_str_mv | AT grahampattison conformationalpreferencesofafluoroketonesmayinfluencetheirreactivity |