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Chemoselectivity Control in the Asymmetric Hydrogenation of γ- and δ-Keto Esters into Hydroxy Esters or Diols
| Title: | Chemoselectivity Control in the Asymmetric Hydrogenation of γ- and δ-Keto Esters into Hydroxy Esters or Diols |
| Authors: | Arai, Noriyoshi Browse this author →KAKEN DB | | Namba, Takanori Browse this author | | Kawaguchi, Kei Browse this author | | Matsumoto, Yuki Browse this author | | Ohkuma, Takeshi Browse this author →KAKEN DB |
| Keywords: | asymmetric catalysis | | chemoselectivity | | hydrogenation | | keto esters | | ruthenium |
| Issue Date: | 26-Jan-2018 |
| Publisher: | Wiley |
| Journal Title: | Angewandte Chemie International Edition |
| Volume: | 57 |
| Issue: | 5 |
| Start Page: | 1386 |
| End Page: | 1389 |
| Publisher DOI: | 10.1002/anie.201711363 |
| PMID: | 29205740 |
| Abstract: | The asymmetric hydrogenation of aromatic γ‐ and δ‐keto esters into optically active hydroxy esters or diols under the catalysis of a novel DIPSkewphos/3‐AMIQ–RuII complex was studied. Under the optimized conditions (8 atm H2 , Ru complex/t‐C4H9OK=1:3.5, 25 °C) the γ‐ and δ‐hydroxy esters (including γ‐lactones) were obtained quantitatively with 97–99 % ee. When the reaction was conducted under somewhat harsh conditions (20 atm H2 , [t‐C4H9OK]=50 mm, 40 °C), the 1,4‐ and 1,5‐diols were obtained predominantly with 95–99 % ee. The reactivity of the ester group was notably dependent on the length of the carbon spacer between the two carbonyl moieties of the substrate. The reaction of β‐ and ϵ‐keto esters selectively afforded the hydroxy esters regardless of the reaction conditions. This catalyst system was applied to the enantioselective and regioselective (for one of the two ester groups) hydrogenation of a γ‐ϵ‐diketo diester into a trihydroxy ester. |
| Rights: | This is the peer-reviewed version of the following article: Angewandte chemie-international edition 57 (5) 1386-1389 2018-01-26, which has been published in final form at https://doi.org/10.1002/anie.201711363. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-Archiving. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/72368 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 大熊 毅
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