Novel Highly Functionalized Benzoylaminocarbothioyl Pyrrolidine from Benzoylisothiocyanate and Substitueted Pyrrolidine Derived From α-Aminoasit Ester via Imine -Azomethine Ylide- 1,3-Dipolar Cycloaddition Cascade

Abstract

A series of novel highly functionalized benzoylaminocarbothioyl pyrrolidines were prepared by the reaction of benzoylisothiocyanate with substitueted pyrrolidine derived from α -aminoasit ester via metal catalsed imine -azomethine ylides-l,3-Dipolar Cycloaddition in excellent yield. An example of chiral version benzoylaminocarbothioyl pyrrolidine were also reported. The chirality oryginated from menthyl acrylate as chiral dipolarophile in the cycloaddition cascade and induced three novell chiral centres.Introduction:

Stabilized Palladium Nanoparticles from Bis-(N-benzoylthiourea) Derived-PdII Complexes as Efficient Catalysts for Sustainable Cross-Coupling Reactions in Water

“…Using the known methodology developed by our group, the amphiphilic palladium complexes 1 and 2 were obtained ( Figure 1 ). For this purpose, the starting endo -prolinates 3 , isolated after 1,3-dipolar cycloaddition [ 15 , 16 , 17 ], were allowed to react with phenyl isothiocyanate in refluxing acetonitrile to obtain compounds 4 in good yields. Finally, chelation was achieved using palladium(II) acetate in methanol at rt for 48 h. Cis -complexes 1 and 2 were isolated in yields depicted in Figure 1 .…”

“…The Suzuki-Miyaura coupling (Scheme 1) between iodobenzene and different arylboronic acids afforded biaryls 5 in high yields (Table 1, entries 12 and 13). The reaction of aryl bromides needed 120 °C to obtain the same range of yields than the corresponding iodoarenes (Table 1, entries [14][15][16]. However, chloroarenes 3 reacted slowly and required higher temperatures (150 °C) to obtain moderate to good chemical yields of 1 Typical procedure: 4-iodoanisole (0.5 mmol), phenylboronic acid (0.75 mmol), K2CO3 (0.75 mmol), 1 (0.2 mol%), water (1.5 mL) were introduced in a pressure tube and warmed in an oil bath at the corresponding temperature for 24 h. 2 Chemical yields isolated after flash chromatography.…”

“…Again, the chlorine atom remained intact in the reaction shown in entries 13 and 14 of Table 2. Bromobenzene and p-bromoanisole reacted with n-butyl acrylate (6a) or styrene (6b) at 120 • C in 8 h (Table 2, entries [15][16][17][18]. This higher temperature was required to obtain almost complete conversions.…”

“…In general, iodoarenes reacted at 100 • C (Table 3, entries 1op and 10-12) and bromoarenes at 110 • C (Table 3, entries 13-15), achieving chemical yields in the same range (80-75%). Despite using 130 • C and reaction times of 24 h, the yields of product 5 were moderate when aryl chlorides were used as starters (Table 3, entries [16][17][18].…”

Biological properties and conformational studies of amphiphilic Pd(II) and Ni(II) complexes bearing functionalized aroylaminocarbo-N-thioylpyrrolinate units

“…According to our experience, concerning the most bioactive structural arrangement, the ligands L1 , L2 , and L3 were selected for this study ( Scheme 1 ). Using the known methodology developed by our group, the starting compounds endo- prolinates 1 , generated by 1,3-dipolar cycloaddition [ 16 , 21 – 22 ], were submitted to the reaction with benzoyl isothiocyanate in refluxing acetonitrile to obtain compounds L1 , L2 and L3 in good yields [ 16 , 21 ]. Due to the very low biological activity of these ligands by themselves, the chelation with nickel(II) and palladium(II) was successfully performed using the corresponding acetate salt in methanol at rt for 48 h, affording cis- L1-M , L2-M , and L3-M in yields depicted in Scheme 1 .…”