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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doaj-5116c774bbc647979a55213332a1a1c72020-11-25T03:02:20ZengMDPI AGMolecules1420-30492020-08-01253902390210.3390/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 |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Mei Kee Kam Akira Sugiyama Ryouta Kawanishi Kazutaka Shibatomi |
| 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 |
| author_facet |
Mei Kee Kam Akira Sugiyama Ryouta Kawanishi Kazutaka Shibatomi |
| author_sort |
Mei Kee Kam |
| title |
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_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_sort |
asymmetric synthesis of tertiary α -hydroxyketones by enantioselective decarboxylative chlorination and subsequent nucleophilic substitution |
| publisher |
MDPI AG |
| series |
Molecules |
| issn |
1420-3049 |
| publishDate |
2020-08-01 |
| 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. |
| 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 |
| work_keys_str_mv |
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