Kiral Diazadioksokaliks[2]aren[2]triazin Bazlı Organokatalizörün Nitrostirenler ile Antronun Enantiyoselektif Michael Tepkimesinde Kullanılması

Year 2024, Volume: 6 Issue: 1, 58 - 68, 30.04.2024

Ummu Ozgun , Hayriye Nevin Genç , Abdulkadir Sırıt

https://doi.org/10.47112/neufmbd.2024.32

Abstract

Kiral, stereoseçici ya da enantiyoseçici sentez olarak tanımlanan asimetrik sentez bir veya daha fazla stereojenik merkez bulunduran kiral bileşiklerin sentezlenmesini sağlayan organik sentez türüdür. Bir molekülün farklı enantiyomerleri genellikle birbirlerinden farklı biyolojik aktivite gösterdiklerinden dolayı, asimetrik sentez konusu ilaç kimyası ve organik kimyada oldukça önemli bir konudur. Kiral özellik göstermeyen bileşiklerden kiral bir bileşik sentezleme yöntemleri arasında en çok tercih edilen yöntemlerden biri kiral katalizör kullanımıdır. Bu çalışmada anthron ve farklı nitrostiren türevlerinin kullanıldığı asimetrik Michael tepkimesinde kullanılmak üzere literatürde bulunmayan bir kiral katalizör sentezlenmiştir. Öncelikle kiral katalizörün başlangıç maddesi olarak literatürde bulunan diazadioksookaliks[2]aren[2]triazin sentezlenmiştir. Sentezlenen başlangıç maddesi ile (S)-(+)-1-siklohekziletilamin tepkimeye sokularak enantiyoselektif tepkimede kiral katalizör olarak kullanılacak olan madde elde edilmiştir. Çalışma süresince yapılan tüm reaksiyonlar ince tabaka kromatografisi ile izlenmiş ve elde edilen maddeler kolon kromatografisi ile saflaştırılmıştır. Saflaştırılan ürünler FTIR, 1H NMR ve 13C NMR ile aydınlatılmış ve optik çevirme açıları ölçülmüştür. Sentezlenen katalizör asimetrik Michael reaksiyonunda denenmiş, yüksek verim ve yüksek enantiyoseçicilik elde edilmiştir (%95 verim ve %98 ee).

Keywords

Organokataliz, Asimetrik sentez, Michael reaksiyonu

Chiral Diazadioxocalix[2]arene[2]triazine-Based Derivative as Organocatalyst for Enantioselective Michael Reaction of Nitrostyrenes with Anthrone

Abstract

Asymmetric synthesis, also known as chiral, enantioselective or stereoselective synthesis, is an organic synthesis which allows the formation of chiral compounds containing one or more stereogenic centers. Since different enantiomers of a molecule usually show different biological activity from each other, asymmetric synthesis is a very important topic in the pharmaceutical industry and organic chemistry. One of the most preferred methods to obtain a chiral compound from non-chiral compounds is the use of chiral catalysts. In this study, a chiral catalyst, which is not available in the literature, was synthesized for use in the asymmetric Michael reaction using anthrone and different nitrostyrene derivatives. First, diazadioxocalix[2]arene[2]triazine, which is available in the literature, was synthesized as the starting material of the chiral catalyst. (S)-(+)-1-cyclohexylethylamine was reacted with the synthesized starting material to obtain the substance to be used as a chiral catalyst in the enantioselective reaction. During the study, all reactions were monitored by thin layer chromatography and the obtained substances were purified by column chromatography. The structures of the purified products were elucidated by FTIR, 1H NMR and 13C NMR techniques and optical rotation angles were measured. The synthesized catalyst was tested in asymmetric Michael reaction and high yields and high enantioselectivity were obtained (95% yield and 98% ee).

Keywords

Asymmetric synthesis, Michael reaction, Organocatalysis

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