Synthesis of cyclohexene substituted azaspirodien compounds by RCM and corresponding tetrahydrospirocyclopenta[c]pyrolidinone compound via PKR
Küçük Resim Yok
Tarih
2021
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Bolu Abant İzzet Baysal Üniversitesi
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Bu bağlamın kapsamı, organik tıbbi ve farmasötik kimyadaki önemi nedeniyle nitrojen atomu içeren birkaç yeni spirosiklik iskelet yapılı bileşiklerin senteziyle ilgilidir. Sikloheksenon ve onun türevleri yüksek miktarda fonksiyonlaştırılmış ayrıca kiral bioaktif önemi nedeniyle başlangıç maddeleri olarak seçilmiştir. İlk olarak sikloheksenon N-allylimin ve N-propargylimin oluşturmak için allylamin veya propargylamin ile reaksiyona sokulur. Daha sonra karşılık gelen dien ve enyne yapıları elde etmek için azot atomu koruma veya korumasız Grinard reaksiyonu yapılır. Sonunda karşılık gelen azaspiroundekadien ve azaspirodekdien karboksilat 81%, 78% sırasıyla elde etmek için halka kapanışı metatezi (HKM) dien yapılarına uygulandı. Diğer taraftan enin yapılarına kobalt karbonil Co2(CO)8 ve N-metil morfolin N-oksit (NMO) varlığında siklopenta[c]peridienon, siklopenta[c]piridienin karboksilat, ve siklopenta[c]pyrolin karboksilat iskeletleri sırasıyla 67%, 75% ve 65% verimlerle elde etmek için Pauson-Khand reaksiyonu (PKR) uygulandı. Son olarak bu bağlamdaki elde edilen tüm bileşikler iminden spirosiklik bileşiklere kadar yenidir ve tüm reaksiyonlar nitrojen atmosferi (N2) altında gerçekleştirilmiştir.
The coverage of this context is related to the synthesis of several novel spirocyclic scaffolds containing nitrogen atom due to their importance in organic medicinal and pharmaceutical chemistry. Cyclohexenone and its derivatives were selected as starting materials due to the presence of these compounds in highly functionalized and important chiral bioactive compounds. First, cyclohexenone was reacted with allylamine or propargyl amine to form N-allyl imine and N-propargyl imine derivatives. Followed by the Grignard addition reaction with/without the protection of nitrogen atom to attain the corresponding diene and enyne structures. Ring Closing Metathesis (RCM) was applied on diene structures to finally attain the corresponding azaspiroundecadiene and azaspirodecadiene carboxylate with 81% and 78% respectively. On the other hand, Pauson-Khand reaction (PKR) was applied on enyne structures in the presence of cobalt carbonyl Co2(CO)8 and N-methyl morpholine N-oxide (NMO) to obtain cyclopenta[c]pyridinenone, cyclopenta[c]pyridinene carboxylate, and cyclopenta[c]pyrroline carboxylate skeletons with 67%, 75% and 65% chemical yields respectively. Finally, all compounds obtained in this context are novel from Imine to spirocyclic compounds and all reactions were carried out under nitrogen atmosphere (N2).
The coverage of this context is related to the synthesis of several novel spirocyclic scaffolds containing nitrogen atom due to their importance in organic medicinal and pharmaceutical chemistry. Cyclohexenone and its derivatives were selected as starting materials due to the presence of these compounds in highly functionalized and important chiral bioactive compounds. First, cyclohexenone was reacted with allylamine or propargyl amine to form N-allyl imine and N-propargyl imine derivatives. Followed by the Grignard addition reaction with/without the protection of nitrogen atom to attain the corresponding diene and enyne structures. Ring Closing Metathesis (RCM) was applied on diene structures to finally attain the corresponding azaspiroundecadiene and azaspirodecadiene carboxylate with 81% and 78% respectively. On the other hand, Pauson-Khand reaction (PKR) was applied on enyne structures in the presence of cobalt carbonyl Co2(CO)8 and N-methyl morpholine N-oxide (NMO) to obtain cyclopenta[c]pyridinenone, cyclopenta[c]pyridinene carboxylate, and cyclopenta[c]pyrroline carboxylate skeletons with 67%, 75% and 65% chemical yields respectively. Finally, all compounds obtained in this context are novel from Imine to spirocyclic compounds and all reactions were carried out under nitrogen atmosphere (N2).
Açıklama
Lisansüstü Eğitim Enstitüsü, Kimya Ana Bilim Dalı
Anahtar Kelimeler
Kimya, Chemistry
