当前位置: X-MOL 学术Angew. Chem. Int. Ed. › 论文详情
Chemoselectivity Control in the Asymmetric Hydrogenation of γ- and δ-Keto Esters into Hydroxy Esters or Diols
Angewandte Chemie International Edition ( IF 11.994 ) Pub Date : 2017-12-28 , DOI: 10.1002/anie.201711363
Noriyoshi Arai, Takanori Namba, Kei Kawaguchi, Yuki Matsumoto, Takeshi Ohkuma

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.

Thumbnail image of graphical abstract

A conditional promise: Chemoselectivity in the asymmetric hydrogenation of γ- and δ-keto esters into the corresponding hydroxy esters/lactones or diols under the catalysis of a novel RuII complex was precisely controlled by changing the reaction conditions (see scheme). The enantiomeric purity of both products was very high (95–99 % ee). β- and ϵ-keto esters were selectively converted into the hydroxy esters regardless of the reaction conditions.

更新日期:2018-01-22

 

Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
分享到
评论: 1
期刊列表
南方科技大学“千人计划学者”讲座教授郑智平团队招聘启事
中山大学功能生物医用材料团队招聘博士后(待遇每年25万起)
华南理工大学生物科学与工程学院青年千人陈庭坚教授课题组招聘启事
东莞理工学院高薪招聘“有机合成/催化”博士后【48万年薪 + 若干科研启动费】
华南理工大学“青年千人”马志强课题组招聘启事
【问答】请问延长锂空气电池寿命的关键因素是什么?
2017年中科院JCR分区化学大类列表
试剂库存管理
化合物查询
down
wechat
bug