鎳及銥金屬錯合物催化合成異??，??，芳香炔及黃烷酮化合物之研究

Nickel and Iridium Catalyzed Synthesis of Isoquinoline, Quinolines, Arylalkynes and Flavanones

帕沙(K. Pajendra Prasad)

指導教授 ： 鄭建鴻

國立清華大學/理學院/化學系/博士(2006年)

https://doi.org/10.6843/NTHU.2006.00180

摘要

ABSTRACT

In this thesis, nickel-catalyzed cyclization reactions and their application in organic synthesis and material science are discussed. Iridium-catalyzed synthesis of flavanones from 2-hydroxyaldehydes is also discussed. For convenience and better clarity, the thesis is divided in to four chapters. The first chapter deals with the synthesis of isoquinolines derivatives, the second chapter depicts the synthesis of quinolines, the third chapter describes the preparation of arylalkynes and fourth chapter explains the synthesis of flavanones.
The nickel-catalyzed annulations of 2-iodobenzaldimines with various alkynes are investigated in the chapter 1. The reaction of 2-iodobenzaldimines and alkynes in presence of nickel-catalyst gave isoquinolines in high yields. The reaction proceeds in one pot under mild conditions. In addition, we found that there are two alkyne insertion pathways for the product formation. In the second chapter a useful method for the construction of quinolines is described. The yields of the quinoline derivatives are good. Based on the regio-selective outcome resulted from the of substitution pattern in the product, a possible reaction mechanism has been proposed. The application of this synthetic methodology is successfully exemplified by synthesizing naturally occurring alkaloids.
In the third chapter synthesis of arylalkynes from diynes is described. The reaction provides a convenient method for the preparation of these derivatives. A wide range of conjugated diynes such as symmetric and unsymmetrical are employed in the reaction. Similarly, a large variety of non-conjugated diynes are employed to test the regio-selectivity in the reaction.

In the fourth chapter flavanone synthesis from 2-hydroxyaldehydes is described. The reaction proceeds under economical conditions such as low catalyst load and utilizes easily available aldehyde derivatives. Another convenient method for the preparation of flavanones is also described from 2-hydroxybenzyl alcohols. The reaction in this case follows three tandem steps namely oxidation, hydroacylation and cyclization. The utility of this method is described.

關鍵字

異喹啉

參考文獻

1. Ni-Catalyzed Highly Regio- and Chemoselective Cocycloaddition of Nonconjugated Diynes with 1,3-Diynes: A Novel Method for Polysubstituted Arylalkynes. Jeevanandam, A.; Korivi, R. P.; Huang, I. W.; Cheng, C-H. Org. Lett. 2002, 4, 807.

2. Highly Efficient Synthesis of Isoquinolines via Nickel-Catalyzed Annulation of 2-Iodobenzaldimines With Alkynes: Evidence for Dual Pathways of Alkyne Insertion. Korivi, R. P.; Cheng, C-H. Org. Lett. 2005, 7, 5179.

3. Nickel-Catalyzed Cyclization of 2-Iodoanilines with Aroylalkynes: An Efficient Route for Quinoline Derivatives. Korivi, R. P.; Cheng, C-H. J. Org. Chem. 2006, Accepted for publication.

4. Iridium-Catalyzed Oxidation, Hydroacylation and Cyclization of 2-hydroxybenzyl alcohols With Alkynes: Resplendent Method for Preparation of Flavanones. Korivi, R. P.; Cheng, C-H. Manuscript under preparation.