[Thu. 22 Sep. 2016] Prof. Anna Lee/Organocatalyzed Asymmetric Reactions

by Manager posted Sep 20, 2016
?

Shortcut

PrevPrev Article

NextNext Article

ESCClose

+ - Up Down Comment Print
Extra Form
Speaker Prof. Anna Lee
Date Thursday 22 September 2016
Time 5:00pm
Venue #331, Asan Hall, College of Science

Organocatalyzed Asymmetric Reactions

 

 

The Catalytic Asymmetric Knoevenagel Condensation: The Knoevenagel condensation reaction developed by Emil Knoevenagel in 1896 is a powerful and efficient carbon-carbon bond forming reaction, but also the root of aminocatalysis. Remarkably though, while the Knoevenagel reaction, as the historic basis of all aminocatalyzed processes, has been incorporated into asymmetric organocascades and domino reactions, and even chiral auxiliary derived malonates have been studied, a variation in which the Knoevenagel reaction itself is utilized to establish asymmetry remained elusive. The main problems of the reaction were reactivity and stereoselectivity issues as well as the formation of by-products. The goal of this work was to develop the first enantioselective Knoevenagel condensation reaction using a novel chiral amine catalyst based on a dynamic kinetic resolution (DKR). Various chiral amine catalysts were synthesized, and we found that modified cinchona based amine catalysts provided the desired product in high yield and enantioselectivity.

 

figure.PNG

 

A Cooperative N-Heterocyclic Carbene/Chiral phosphate Catalysis System for Allenolate Annulations: NHC-catalyzed homoenolate additions to various electrophiles represent an enabling class of transformations that have been employed for the construction of complex hetero- and carbocyclic system through unconventional Umpolung reactivity. Recently, our group developed Lewis acid/NHC cooperative catalysis to develope novel transformations. In this study, we have extended the scope of cooperative catalysis by employing chiral phosphoric acids for the first time and this novel cooperative catalysis was applied to the challenging allenolate annulation reaction (Figure 1). A limited number of reports of NHC-catalyzed homoenolate additions involving alkynyl aldehydes have appeared. We have developed a highly efficient asymmetric [3+2] annulation reaction of alkynyl aldehydes withα-ketoesters via NHC/chiral phosphate cooperative catalysis.

 

figure2.PNG

 

 

 

 

References

1. Lee, A.; Michrowska, A.; S.-Mosse, S.; List, B., Angew. Chem. Int. Ed. 2011, 50, 1707.

2. Lee, A.; Reisinger, C.; List, B., Adv. Synth. Catal. 2012, 354, 1701.

3. Lee, A.; Scheidt, K. A., Angew. Chem. Int. Ed. 2014, 53, 7594.

4. Lee, A.; Younai, A. ; Price, C. K. ; Izquierdo, J. ; Mishra, R. K. ; Scheidt, K. A., J. Am. Chem. Soc. 2014,136, 10589.

5. Lee, A.; Scheidt, K. A., Chem. Commun. 2015, 51, 3407.

 

 

Prof. Anna Lee

Myongji University, Department of Chemistry, Yongin, Korea

 

 


Articles

1 2 3 4 5 6 7 8

Designed by sketchbooks.co.kr / sketchbook5 board skin

나눔글꼴 설치 안내


이 PC에는 나눔글꼴이 설치되어 있지 않습니다.

이 사이트를 나눔글꼴로 보기 위해서는
나눔글꼴을 설치해야 합니다.

설치 Cancel

Sketchbook5, 스케치북5

Sketchbook5, 스케치북5

Sketchbook5, 스케치북5

Sketchbook5, 스케치북5