Journal
CHEMICAL & PHARMACEUTICAL BULLETIN
Volume 59, Issue 1, Pages 1-22Publisher
PHARMACEUTICAL SOC JAPAN
DOI: 10.1248/cpb.59.1
Keywords
rare earth metal; asymmetric catalysis; atom economy; proton transfer; tetrasubstituted stereogenic center
Funding
- Japan Society for the Promotion of Science
- Japanese Ministry of Education Culture Sports Science and Technology
- Synthetic Organic Chemistry Mitsubishi Chemical Corporation
- Sankyo Foundation for Life Sciences
- Sumitomo Foundation
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The development of atom-economical catalytic asymmetric reactions based on two distinct sets of catalyst, a rare earth metal/amide-based ligand catalyst and a soft Lewis acid/hard Bronsted base catalyst, is reviewed These catalytic systems exhibit high catalytic activity and stereoselectivity by harnessing a cooperative catalysis through hydrogen bond/metal coordination and soft soft interactions/hard hard interactions, respectively The effectiveness of these cooperative catalysts is clearly delineated by the high stereoselectivity in reactions with highly coordinative substrates, and the specific activation of otherwise low-reactive pronucleophiles under proton transfer conditions The rare earth metal/amide-based ligand catalyst was successfully applied to catalytic asymmetric aminations, nitroaldol (Henry) reactions, Mannich-type reactions, and conjugate addition reactions, generating stereogenic tetrasubstituted centers Catalytic asymmetric amination and anti-selective catalytic asymmetric nitroaldol reactions were successfully applied to the efficient enantioselective synthesis of therapeutic candidates, such as AS-3201 and the beta(3)-adrenoreceptor agonist, showcasing the practical utility of the present protocols The soft Lewis acid/hard Bronsted base cooperative catalyst was specifically developed for the chemoselective activation of soft Lewis basic allylic cyanides and thioamides, which are otherwise low-reactive pronucleophiles The cooperative action of the catalyst allowed for efficient catalytic generation of active carbon nucleophiles in situ, which were integrated Into subsequent enantioselective additions to carbonyl-type electrophiles
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