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鈷金屬催化具高立體選擇性之[3+2]環化反應以合成茚胺衍生物之研究
Dissertation

鈷金屬催化具高立體選擇性之[3+2]環化反應以合成茚胺衍生物之研究

陳旻賢
Doctor of Philosophy (PHD), 國立清華大學, 化學系
2013

Abstract

不對稱催化 [3+2]環化 茚胺 具立體選擇性的 cobalt asymmetric catalysis [3+2] annulation aminoindene stereoselective
In this thesis, we successfully develop cobalt-catalyzed [3+2] annulation reactions of imine with unsaturated bonds and synthesize aminoindane-and indenes derivatives with efficiency. By these methodologies, we can construct aminoindane or indene skeletons in one step and it is also powerful synthetic methods for the synthesis of relative aminoindane or indene natural product and drugs. In chapter 2, we develop cobalt-catalyzed [3+2] annulation of 2-iminoarylboronic acids with conjugate alkenes to synthesize aminoindane carboxylate derivatives with high chemo-and diastereoselectivity. In chapter 3, we extend the result of chapter 2 and synthesize aminoindene derivatives by cobalt-catalyzed [3+2] annulation of 2-iminoarylboronic acids with alkynes. Furthermore, we combine PHOX chiral ligands which are prepared from commercial available amino acids in the cobalt catalysis reaction and generate a series of chiral aminoindenes with high regio-and enantioselectivity. In the final chapter, based on our cobalt catalysis system of aryl halides with other substrates experience before, we develop cobalt-catalyzed asymmetric [3+2] annulation of 2-iminoarylbromides with alkynes to construct chiral aminoindenes. In this reaction, we can prepare multi-substituted chiral aminoindenes with good to excellent regio-and enantioselectivity. Besides, we can learn more about the relative position of chiral cobalt complex and substrates in the reaction environment via absolute configuration determination.

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