Asymmetric Synthesis of Tertiary α -Hydroxyketones by Enantioselective Decarboxylative Chlorination and Subsequent Nucleophilic Substitution
Chiral tertiary α-hydroxyketones were synthesized with high enantiopurity by asymmetric decarboxylative chlorination and subsequent nucleophilic substitution. We recently reported the asymmetric decarboxylative chlorination of β-ketocarboxylic acids in the presence of a chiral primary amine catalyst...
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MDPI AG
2020-08-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/17/3902 |
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| author | Mei Kee Kam Akira Sugiyama Ryouta Kawanishi Kazutaka Shibatomi |
| author_facet | Mei Kee Kam Akira Sugiyama Ryouta Kawanishi Kazutaka Shibatomi |
| author_sort | Mei Kee Kam |
| collection | DOAJ |
| description | Chiral tertiary α-hydroxyketones were synthesized with high enantiopurity by asymmetric decarboxylative chlorination and subsequent nucleophilic substitution. We recently reported the asymmetric decarboxylative chlorination of β-ketocarboxylic acids in the presence of a chiral primary amine catalyst to obtain α-chloroketones with high enantiopurity. Here, we found that nucleophilic substitution of the resulting α-chloroketones with tetrabutylammonium hydroxide yielded the corresponding α-hydroxyketones without loss of enantiopurity. The reaction proceeded smoothly even at a tertiary carbon. The proposed method would be useful for the preparation of chiral tertiary alcohols. |
| first_indexed | 2024-03-10T16:46:49Z |
| format | Article |
| id | doaj.art-5116c774bbc647979a55213332a1a1c7 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T16:46:49Z |
| publishDate | 2020-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-5116c774bbc647979a55213332a1a1c72023-11-20T11:32:15ZengMDPI AGMolecules1420-30492020-08-012517390210.3390/molecules25173902Asymmetric Synthesis of Tertiary α -Hydroxyketones by Enantioselective Decarboxylative Chlorination and Subsequent Nucleophilic SubstitutionMei Kee Kam0Akira Sugiyama1Ryouta Kawanishi2Kazutaka Shibatomi3Department of Applied Chemistry and Life Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi 441-8580, JapanDepartment of Applied Chemistry and Life Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi 441-8580, JapanDepartment of Applied Chemistry and Life Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi 441-8580, JapanDepartment of Applied Chemistry and Life Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi 441-8580, JapanChiral tertiary α-hydroxyketones were synthesized with high enantiopurity by asymmetric decarboxylative chlorination and subsequent nucleophilic substitution. We recently reported the asymmetric decarboxylative chlorination of β-ketocarboxylic acids in the presence of a chiral primary amine catalyst to obtain α-chloroketones with high enantiopurity. Here, we found that nucleophilic substitution of the resulting α-chloroketones with tetrabutylammonium hydroxide yielded the corresponding α-hydroxyketones without loss of enantiopurity. The reaction proceeded smoothly even at a tertiary carbon. The proposed method would be useful for the preparation of chiral tertiary alcohols.https://www.mdpi.com/1420-3049/25/17/3902chlorinationS<sub>N</sub>2 reactionasymmetric synthesisorganocatalysttertiary alcoholsα-hydroxyketones |
| spellingShingle | Mei Kee Kam Akira Sugiyama Ryouta Kawanishi Kazutaka Shibatomi Asymmetric Synthesis of Tertiary α -Hydroxyketones by Enantioselective Decarboxylative Chlorination and Subsequent Nucleophilic Substitution Molecules chlorination S<sub>N</sub>2 reaction asymmetric synthesis organocatalyst tertiary alcohols α-hydroxyketones |
| title | Asymmetric Synthesis of Tertiary α -Hydroxyketones by Enantioselective Decarboxylative Chlorination and Subsequent Nucleophilic Substitution |
| title_full | Asymmetric Synthesis of Tertiary α -Hydroxyketones by Enantioselective Decarboxylative Chlorination and Subsequent Nucleophilic Substitution |
| title_fullStr | Asymmetric Synthesis of Tertiary α -Hydroxyketones by Enantioselective Decarboxylative Chlorination and Subsequent Nucleophilic Substitution |
| title_full_unstemmed | Asymmetric Synthesis of Tertiary α -Hydroxyketones by Enantioselective Decarboxylative Chlorination and Subsequent Nucleophilic Substitution |
| title_short | Asymmetric Synthesis of Tertiary α -Hydroxyketones by Enantioselective Decarboxylative Chlorination and Subsequent Nucleophilic Substitution |
| title_sort | asymmetric synthesis of tertiary α hydroxyketones by enantioselective decarboxylative chlorination and subsequent nucleophilic substitution |
| topic | chlorination S<sub>N</sub>2 reaction asymmetric synthesis organocatalyst tertiary alcohols α-hydroxyketones |
| url | https://www.mdpi.com/1420-3049/25/17/3902 |
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