Cinchona urea compounds having 3,5-diiodophenyl moieties were subjected to Yamamoto coupling polymerization to afford the chiral urea polymers. These polymers showed high activities as heterogeneous catalysts in asymmetric Michael reactions comparable with those of the corresponding monomeric catalyst in solution systems. Furthermore, the polymeric catalysts are easily recovered from their reaction mixtures due to their insolubility and can be reused several times without loss of catalytic activity.
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http://dx.doi.org/10.1002/chir.23526 | DOI Listing |
Chemistry
November 2024
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N Zhongshan Road, Shanghai, 200062, China.
We report an H-bond donor controlled diastereoselective switchable intramolecular aza-Henry reaction of ketimines derived from α-ketoesters and 2-(2-nitroethyl)anilines, allowing facile access to chiral tetrahydroquinolines bearing an aza-quaternary carbon stereocenter, which are privileged scaffold for medicinal researches. While newly developed cinchona alkaloid derived phosphoramide-bearing quaternary ammonium salt C2 selectively give cis-adducts in up to 20 : 1 dr and 99 % ee, the corresponding urea-bearing analogue C8 preferentially give trans-adducts in up to 20 : 1 dr and 99 % ee.
View Article and Find Full Text PDFYakugaku Zasshi
July 2024
Faculty of Pharmacy, Meijo University.
This review describes novel organocatalytic methods for the enantioselective construction of spiroindans and spirochromans and the application of the methods to the total synthesis of natural products. We developed an intramolecular Friedel-Craftstype 1,4-addition in which the substrates were a resorcinol derivative and 2-cyclohexenone linked by an alkyl chain. The reaction proceeded smoothly in the presence of a cinchonidine-based primary amine (30 mol%) with water and p-bromophenol as additives.
View Article and Find Full Text PDFChirality
March 2023
Gifu College, National Institute of Technology, Gifu, Japan.
Cinchona urea compounds having 3,5-diiodophenyl moieties were subjected to Yamamoto coupling polymerization to afford the chiral urea polymers. These polymers showed high activities as heterogeneous catalysts in asymmetric Michael reactions comparable with those of the corresponding monomeric catalyst in solution systems. Furthermore, the polymeric catalysts are easily recovered from their reaction mixtures due to their insolubility and can be reused several times without loss of catalytic activity.
View Article and Find Full Text PDFChem Rec
July 2023
Institute of Organic Chemistry, Johannes Kepler University Linz, Altenbergerstrasse 69, 4040, Linz, Austria.
(Thio)-urea-containing bifunctional quaternary ammonium salts emerged as powerful non-covalently interacting organocatalysts over the course of the last decade. The most commonly employed catalysts in this field are either based on Cinchona alkaloids, α-amino acids, or trans-cyclohexane-1,2-diamine. Our group has been heavily engaged in the design and use of such catalysts, i.
View Article and Find Full Text PDFOrg Lett
March 2022
Research Institute of Pharmaceutical Sciences and College of Pharmacy, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Republic of Korea.
The highly enantioselective aza-Michael reaction of -butyl β-naphthylmethoxycarbamate to cyclic enones has been accomplished by using a new alkaloid derived C(9)-urea ammonium catalyst under phase-transfer catalysis conditions with up to 98% ee at 0 °C. The resulting aza-Michael adducts can be converted to versatile intermediates by selective deprotection and the cyclic 1,3-aminoalcohols by diastereoselective reduction with up to 32:1, which have been widely used as important pharmacophores in pharmaceutical development.
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