The Reduction of Carbonyl Compounds with Dicyclopentylzinc: A New Example of Asymmetric Amplifying Autocatalysis
A previously unknown reduction of carbonyl compounds with dicyclopentylzinc is reported. Aldehydes react in mild conditions yielding corresponding primary alcohols and cyclopentene. Although cyclohexanone and acetophenone are inert to dicyclopentylzinc, a variety of heterocyclic ketones reacted read...
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2023-12-01
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| Series: | International Journal of Molecular Sciences |
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| author | Elena Sh. Saigitbatalova Liliya Z. Latypova Almaz A. Zagidullin Almira R. Kurbangalieva Ilya D. Gridnev |
| author_facet | Elena Sh. Saigitbatalova Liliya Z. Latypova Almaz A. Zagidullin Almira R. Kurbangalieva Ilya D. Gridnev |
| author_sort | Elena Sh. Saigitbatalova |
| collection | DOAJ |
| description | A previously unknown reduction of carbonyl compounds with dicyclopentylzinc is reported. Aldehydes react in mild conditions yielding corresponding primary alcohols and cyclopentene. Although cyclohexanone and acetophenone are inert to dicyclopentylzinc, a variety of heterocyclic ketones reacted readily, yielding reasonable to high yields of corresponding secondary alcohols. When the reaction was catalyzed with (–)-(1<i>R</i>,2<i>S</i>)-ephedrine, 3-acetylpyridine (<b>10</b>) resulted in a high yield of (<i>S</i>)-1-(pyridin-3-yl)ethanol (<b>19</b>) with >99% ee. 5-Acetyl-2-bromopyridine (<b>11</b>) also provided the corresponding optically active alcohol <b>20</b>, albeit with a much lower optical yield. When 10% of <b>19</b> with 92% ee was used as an autocatalyst, 55% yield of the same compound was obtained, with 95% ee and 96% ee in two independent experiments. A three-stage reaction sequence starting from “no chirality” reaction yielded <b>19</b> with 6% ee. Thus, amplifying autocatalysis was detected in the reaction of ketone <b>10</b> with dicylopentylzinc. |
| first_indexed | 2024-03-09T01:48:46Z |
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| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-09T01:48:46Z |
| publishDate | 2023-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-48ef941031b449fc82bb90997b8c35dc2023-12-08T15:18:11ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-12-0124231704810.3390/ijms242317048The Reduction of Carbonyl Compounds with Dicyclopentylzinc: A New Example of Asymmetric Amplifying AutocatalysisElena Sh. Saigitbatalova0Liliya Z. Latypova1Almaz A. Zagidullin2Almira R. Kurbangalieva3Ilya D. Gridnev4Biofunctional Chemistry Laboratory, A. Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlyovskaya Street, 420008 Kazan, RussiaBiofunctional Chemistry Laboratory, A. Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlyovskaya Street, 420008 Kazan, RussiaA. E. Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Street, 420088 Kazan, RussiaBiofunctional Chemistry Laboratory, A. Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlyovskaya Street, 420008 Kazan, RussiaN. D. Zelinsky Institute of Organic Chemistry, Leninsky Prosp. 47, 119991 Moscow, RussiaA previously unknown reduction of carbonyl compounds with dicyclopentylzinc is reported. Aldehydes react in mild conditions yielding corresponding primary alcohols and cyclopentene. Although cyclohexanone and acetophenone are inert to dicyclopentylzinc, a variety of heterocyclic ketones reacted readily, yielding reasonable to high yields of corresponding secondary alcohols. When the reaction was catalyzed with (–)-(1<i>R</i>,2<i>S</i>)-ephedrine, 3-acetylpyridine (<b>10</b>) resulted in a high yield of (<i>S</i>)-1-(pyridin-3-yl)ethanol (<b>19</b>) with >99% ee. 5-Acetyl-2-bromopyridine (<b>11</b>) also provided the corresponding optically active alcohol <b>20</b>, albeit with a much lower optical yield. When 10% of <b>19</b> with 92% ee was used as an autocatalyst, 55% yield of the same compound was obtained, with 95% ee and 96% ee in two independent experiments. A three-stage reaction sequence starting from “no chirality” reaction yielded <b>19</b> with 6% ee. Thus, amplifying autocatalysis was detected in the reaction of ketone <b>10</b> with dicylopentylzinc.https://www.mdpi.com/1422-0067/24/23/17048Soai reactionchirality amplificationdicyclopentylzincDFTheterocyclic ketonesasymmetric autocatalysis |
| spellingShingle | Elena Sh. Saigitbatalova Liliya Z. Latypova Almaz A. Zagidullin Almira R. Kurbangalieva Ilya D. Gridnev The Reduction of Carbonyl Compounds with Dicyclopentylzinc: A New Example of Asymmetric Amplifying Autocatalysis International Journal of Molecular Sciences Soai reaction chirality amplification dicyclopentylzinc DFT heterocyclic ketones asymmetric autocatalysis |
| title | The Reduction of Carbonyl Compounds with Dicyclopentylzinc: A New Example of Asymmetric Amplifying Autocatalysis |
| title_full | The Reduction of Carbonyl Compounds with Dicyclopentylzinc: A New Example of Asymmetric Amplifying Autocatalysis |
| title_fullStr | The Reduction of Carbonyl Compounds with Dicyclopentylzinc: A New Example of Asymmetric Amplifying Autocatalysis |
| title_full_unstemmed | The Reduction of Carbonyl Compounds with Dicyclopentylzinc: A New Example of Asymmetric Amplifying Autocatalysis |
| title_short | The Reduction of Carbonyl Compounds with Dicyclopentylzinc: A New Example of Asymmetric Amplifying Autocatalysis |
| title_sort | reduction of carbonyl compounds with dicyclopentylzinc a new example of asymmetric amplifying autocatalysis |
| topic | Soai reaction chirality amplification dicyclopentylzinc DFT heterocyclic ketones asymmetric autocatalysis |
| url | https://www.mdpi.com/1422-0067/24/23/17048 |
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