Pirolidin ve oksimlerin benzoilizotiyosiyanat ile tepkimeleri sonucu yeni bileşiklerin sentezi, yapılarının aydınlatılması

Abstract

oz Bu çalışmada, farklı aminoasit esterlerinden çıkılarak imin azometin ylid 1,3- dipolar halkalı katılmaları sonucu sübstitüe pirolidin türevleri sentezlendi. Sentezlenen pirolidin türevlerinin benzoilizotiyosiyanatla tepkimesi sonucu yüksek verimle pirolidin halkası içeren potansiyel biyoaktif yeni akiral 1- benzoilaminokarbotiyol-5-fenil-pirolidin-2,4-dikarboksilik asit dimetil esteri (BT1), l-benzoilaminokarbotiyol-2,5-difenil-pirolidin-2,4-dikarboksilik asit dimetil esteri (BT ), l-benzoilaminokarbotiyol-2-benzil-5-fenil-pirolidin-2,4-dikarboksilik asit dimetil esteri (BT3) ve kiral (2S,4S,5R)-l-benzoilaminokarbotiyol-2-metil-5-fenil- pirolidin-2,4-dikarboksilik asit 4-((lR,2S,5R)-2-izopropiİ-5-metil-siklohekzü) ester 2-metil esteri (BT4) bileşikleri sentezlendi. Elde edilen bileşiklerin yapılan 'H-NMR, 13C-NMR, 2D-COSY, DEPT, FT-IR ve MS gibi teknikler ile aydınlatıldı. Bununla birlikte bu çalışmada, oksimlerin benzoilizotiyosiyanatla tepkimelerinin incelenmesi ve sentezlenen £-benzaldehit 0-benzoiloksim (BO1), E- anisolaldehit O-benzoiloksim (BO2) ve Z- nitron bileşiklerinin yukarıda bahsedilen teknikler ve X-ray tek kristal teknikleri ile karakterizasyonu yapıldı. Anahtar Kelimeler: Polisübstitüe pirolidin türevleri; benzoilizotiyosiyanat; benzoilaminokarbotiyol pirolidinler; ls-benzaldehit O-benzoiloksim; imine-azometin ylid 1,3-dipolar halkalı katılmalar; oksim ve nitron.

ABSTRACT A series of novel highly functionalized potential bioactive benzoylaminocarbothioyl pyrrolidines 1 -Benzoylaminocarbothioyl-5-phenyl- pyrrolidine-2,4-dicarboxylic acid dimethyl ester (BT1), 1-Benzoylaminocarbothioyl- 2,5-diphenyl-pyrrolidine-2,4-dicarboxylic acid dimethyl ester (BT2), 1- Benzoylaminocarbotbioyl-2-ben2yl-5-phenyl-pyrrolidine-2,4-dicarboxylic acid dimethyl ester (BT ) were prepared by the reaction of benzoylisothiocyanate with substitued pyrrolidine derived from a -aminoasit ester via metal catalsed imine - azomethine ylides-l,3-dipolar cycloaddition in excellent yield. An example of chiral version benzoylaminocarbothioyl pyrrolidine, (2S,4S,5R)-1- Benzoylaminocarbothioyl-2-methyl-5 -phenyl-pyrrolidine-2,4-dicarboxylic acid 4- ((lR,2S,5R)-2-isopropyl-5-methyl-cyclohexyl) ester 2-methyl ester (BT4), were also reported. The chirality originated from menthyl acrylate as chiral dipolarophile in the cycloaddition cascade and induced three novel chiral centres. In addition to that a series of novel aldehyde 0-benzoyloximes and nitrones were prepared, from a novel methodology, by the reaction of benzoylisothiocyanate and oxime derivatives. Two examples of nitrone formation by the reaction of Z- oximes and benzoylisothiocyanate were also reported. The structures of prepared novel compounds were detemined by ^-NMR, 13C-NMR, 2D-COSY, DEPT, FT-IR, MS, X-ray and micro analyses. Keywords: Polysubstitued pyrrolidine derivatives; benzoylisothiocyanate; benzoylaminocarbothioyl pyrrolidines; E- aldehyde 0-benzoyloximes; imine- azometin ylide 1,3-dipole cycloaddition reactions, oxime and nitrone. II