Please use this identifier to cite or link to this item: https://hdl.handle.net/11147/5712
Title: Synthesis of vinylallenols via palladium-caralyzed arylation reactions of (Z)-2,4-enyne oxiranes with organoborons
Other Titles: (Z)-2,4-Enin oksiranların organoboronlar ile paladyum katalizli arilasyon tepkimeleri üzerinden vinilallenollerin sentezi
Authors: Artok, Levent
Ziyanak, Fırat
Keywords: Palladium
Organoborons
Synthesis (Chemistry)
Allenes
Issue Date: Dec-2016
Publisher: Izmir Institute of Technology
Source: Ziyanak, F. (2016). Synthesis of vinylallenols via palladium-caralyzed arylation reactions of (Z)-2,4-enyne oxiranes with organoborons. Unpublished doctoral dissertation, İzmir Institute of Technology, İzmir, Turkey
Abstract: Allenes are important functional groups especially in synthetic organic chemistry. Due to their unique reactivity and high level of chirality transfer, allenes can be used as building blocks in the synthesis of complex molecules. In recent decades transition-metal catalyzed synthesis of allenes with organometallic reagents has become attractive method. For the synthesis of functionalized allenes, addition of different nucleophiles with the help of various transition metals to propargylic compounds bearing a leaving group has been mostly used. Transition metals are crucial for these reactions for shifting them from SN2 to SN2’ for the formation of allenes. Within the context of this research, a novel palladium-catalyzed arylation reactions of (Z)-2,4-enyne oxiranes with organoborons have been investigated. As a result of the 1,5-substitution reaction, aryl-substituted vinylallenes bearing a hydroxyl group on the allylic position (7-aryl-3,5,6-trien-2-ol) were obtained in high yields and diastereoselectivities. We were able to also disclose that Diels-Alder adducts could be obtained with excellent endo and facial selectivities when the vinylallen types of this study were reacted with dienophiles.
Allenler özellikle sentetik organik kimyada önemli fonksiyonel gruplardır. Benzersiz reaktiviteleri ve yüksek seviyede kiralite transferinden dolayı allenler komplex moleküllerin sentezinde yapıtaşları olarak kullanılabilirler. Son yıllarda, orgonometalik bileşikler ile geçiş metal katalizli allen sentezleri ilgi çekici hale gelmiştir. Fonksiyonlandırılmış allenler, bir ayrılan grup içeren proparjilik bileşiklerine geçiş metallerin yardımıyla çeşitli nükleofillerin katılması ile sentezlenmektedir. Geçiş metalleri bu tür reaksiyonları SN2 den SN2’ e kaydırarak allen oluşturması açısından çok büyük öneme sahiptir. Bu çalışma kapsamında, (Z)-2,4-enin oksiran yapılarının organoboronlar ile paladyum katalizli arilasyon tepkimleri üzerine çalışılmıştır. 1,5-yerdeğiştirme reaksiyonu sonucunda aril bağlı ve allilik pozisyonunda hidroksil grubu taşıyan vinilallenler (7-aril-3,5,6-trien-2-ol) yüksek verim ve diastereoseçimli olarak elde edilebilmiştir. Ayrıca bu çalışmada elde edilen vinilallen tipinin dienofiller ile yüksek endo ve fasiyal seçimli olarak Diels-Alder katılma ürünü elde edilebilmiştir.
Description: Thesis (Doctoral)--İzmir Institute of Technology, Chemistry, İzmir, 2016
Full text release delayed at author's request until 2018.01.23
Includes bibliographical references (leaves: 83-85)
Text in English; Abstract: Turkish and English
xii, 204 leaves
URI: http://hdl.handle.net/11147/5712
Appears in Collections:Phd Degree / Doktora

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