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Chemoselectivity Control in the Asymmetric Hydrogenation of γ‐ and δ‐Keto Esters into Hydroxy Esters or Diols
Author(s) -
Arai Noriyoshi,
Namba Takanori,
Kawaguchi Kei,
Matsumoto Yuki,
Ohkuma Takeshi
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201711363
Subject(s) - chemoselectivity , chemistry , enantioselective synthesis , regioselectivity , catalysis , substrate (aquarium) , reactivity (psychology) , asymmetric hydrogenation , organic chemistry , diol , reaction conditions , biocatalysis , medicinal chemistry , reaction mechanism , medicine , oceanography , alternative medicine , pathology , geology
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–Ru II complex was studied. Under the optimized conditions (8 atm H 2 , Ru complex/ t ‐C 4 H 9 OK=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 H 2 , [ t ‐C 4 H 9 OK]=50 m m , 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.