Asymmetric Synthesis of Tetrahydroquinolinesvia1,5-Hydride Transfer/Cyclization Catalyzed by Chiral Primary Amine Catalysts

2013 ◽  
Vol 355 (16) ◽  
pp. 3131-3136 ◽  
Author(s):  
Young Ku Kang ◽  
Dae Young Kim
Keyword(s):  
Asymmetric Synthesis ◽  
Primary Amine ◽  
Hydride Transfer ◽  
Amine Catalysts

Regio-, Stereo- and Enantioselective α-Addition of Carbonyl Nucleo-philes to Allenamides Catalyzed by a Synergistic Copper/Enamine System

2020 ◽  
Author(s):  
Rémi Blieck ◽  
Sebastien Lemouzy ◽  
Marc Taillefer ◽  
Florian Monnier
Keyword(s):  
Catalytic System ◽  
Secondary Amine ◽  
Primary Amine ◽  
Synergistic Catalysis ◽  
Enantioselective Addition ◽  
Amine Catalysts

A dual copper/enamine catalytic system is found to enable an intermolecular enantioselective α-addition of various carbonyl nucleophiles to allenamides. Secondary amine catalysts allowed the highly enantioselective addition of aldehydes, while using primary amine catalysts led to the enantioselective addition of ketoester nucleophiles. The process was found to be highly regio-, stereo- and enantio-selective and represented the first allene hydrofunctionalization using an synergistic catalysis involving copper

Carbonyl catalysis enables a biomimetic asymmetric Mannich reaction

Science ◽  
2018 ◽  
Vol 360 (6396) ◽  
pp. 1438-1442 ◽  
Author(s):  
Jianfeng Chen ◽  
Xing Gong ◽  
Jianyu Li ◽  
Yingkun Li ◽  
Jiguo Ma ◽  
...  
Keyword(s):  
Asymmetric Synthesis ◽  
High Activity ◽  
Asymmetric Catalysis ◽  
Carbonyl Group ◽  
Mannich Reaction ◽  
Primary Amine ◽  
Chiral Amines ◽  
Carbonyl Groups ◽  
Diphenylphosphinyl Imines

Chiral amines are widely used as catalysts in asymmetric synthesis to activate carbonyl groups for α-functionalization. Carbonyl catalysis reverses that strategy by using a carbonyl group to activate a primary amine. Inspired by biological carbonyl catalysis, which is exemplified by reactions of pyridoxal-dependent enzymes, we developed an N-quaternized pyridoxal catalyst for the asymmetric Mannich reaction of glycinate with aryl N-diphenylphosphinyl imines. The catalyst exhibits high activity and stereoselectivity, likely enabled by enzyme-like cooperative bifunctional activation of the substrates. Our work demonstrates the catalytic utility of the pyridoxal moiety in asymmetric catalysis.

scholarly journals Asymmetric Synthesis of Tertiary α -Hydroxyketones by Enantioselective Decarboxylative Chlorination and Subsequent Nucleophilic Substitution

Molecules ◽  
2020 ◽  
Vol 25 (17) ◽  
pp. 3902
Author(s):  
Mei Kee Kam ◽  
Akira Sugiyama ◽  
Ryouta Kawanishi ◽  
Kazutaka Shibatomi
Keyword(s):  
Asymmetric Synthesis ◽  
Nucleophilic Substitution ◽  
Primary Amine ◽  
Tetrabutylammonium Hydroxide ◽  
Tertiary Alcohols ◽  
Tertiary Carbon ◽  
Chiral Tertiary Alcohols

Chiral tertiary α-hydroxyketones were synthesized with high enantiopurity by asymmetric decarboxylative chlorination and subsequent nucleophilic substitution. We recently reported the asymmetric decarboxylative chlorination of β-ketocarboxylic acids in the presence of a chiral primary amine catalyst to obtain α-chloroketones with high enantiopurity. Here, we found that nucleophilic substitution of the resulting α-chloroketones with tetrabutylammonium hydroxide yielded the corresponding α-hydroxyketones without loss of enantiopurity. The reaction proceeded smoothly even at a tertiary carbon. The proposed method would be useful for the preparation of chiral tertiary alcohols.

Highly Enantioselective Directsyn- andanti-Aldol Reactions of Dihydroxyacetones Catalyzed by Chiral Primary Amine Catalysts

2008 ◽  
Vol 10 (4) ◽  
pp. 653-656 ◽  
Author(s):  
Sanzhong Luo ◽  
Hui Xu ◽  
Long Zhang ◽  
Jiuyuan Li ◽  
Jin-Pei Cheng
Keyword(s):  
Primary Amine ◽  
Aldol Reactions ◽  
Amine Catalysts
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