Pirolidinski derivati u organokatalitičkim transformacijama
Pyrrolidine derivatives in organocatalytic transformations
Аутори
Jovanović, Predrag M.Остала ауторства
Savić, VladimirTešević, Vele
Ferjančić, Zorana
Maslak, Veselin
Nikodinović-Runić, Jasmina
Докторска теза (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
Hiralni, polisupstituisani derivati pirolidina, dobijeni cikloadicionim reakcijamaazometinskih ilida, proučavani su kao organokatalizatori u Michael-ovoj reakciji aldehida/ketonai vinil-sulfona. Pod optimalnim reakcionim uslovima, u kojima se koristilo 10 mol % katalizatorau vlažnom metilen-hloridu prinosi reakcija su generalno bili dobri dok je enantioselektivnostvarirala dostižući 52 %.Razvijen je efikasan biokatalizator za asimetričnu Michael-ovu adiciju acetaldehida na β-nitrostiren na bazi celih ćelija koja eksprimira 4-oksalokrotonat tautomerazu (4-OT). Utvrđen jeoptimalan odnos supstrata i biokatalizatora. Kada je kao supstrat korišćen β-nitrostiren dobijenaje odlična enantioselektivnost (e.e. >99%) uz prinos reakcije do 60%. Biokatalizator je manjeefikasan sa p-hlor-, o-hlor- i p-fluor-β-nitrostirenom gde su dobijeni prinosi od 38%, 51%, 31% ie.e. 84%, 88%, 94%...
Chiral, polysubstituted pirrolydines derivatives, obtained via cycloaddition reactions ofazomethine ylides, were studied as organocatalysts in the Michael reaction of aldehydes/ketonesand vinylsulphones. Under optimised reaction conditions employing 10 mol % of the catalyst inwet CH2Cl2, the yields of the products were generally good while the enantioselectivity varied,reaching up to 52 %.A novel whole cell system based on recombinantly expressed 4-oxalocrotonatetautomerase (4-OT) was developed and shown to be an effective biocatalyst for the asymmetricMichael addition of acetaldehyde to β-nitrostyrenes. Optimal ratio of substrates and biocatalystwas determined. Excellent enantioselectivity (>99% ee) and product yields of up to 60% wereobtained with β-nitrostyrene substrate. The biocatalyst exhibited lower reaction rates with pchloro-,o-chloro- and p-fluoro-β-nitrostyrenes with product yields of 38%, 51%, 31% and eevalues of 84%, 88% and 94% respectively...
Кључне речи:
organocatalysis / proline derivatives / thiourea derivatives / 4-Oxalocrotonatetautomerase / Michael reaction / enantioselectivity / biocatalysis / Escherichia coli / organokataliza / derivati prolina / derivati tiouree / 4-oksalokrotonattautomeraza / Michael-ova reakcija / enantioselektivnost / biokataliza / Escherichia coliИзвор:
Универзитет у Београду, 2017Издавач:
- Универзитет у Београду, Хемијски факултет
URI
http://eteze.bg.ac.rs/application/showtheses?thesesId=5057https://fedorabg.bg.ac.rs/fedora/get/o:15788/bdef:Content/download
http://vbs.rs/scripts/cobiss?command=DISPLAY&base=70036&RID=49041935
http://nardus.mpn.gov.rs/123456789/8300
https://cherry.chem.bg.ac.rs/handle/123456789/2733
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - THES AU - Jovanović, Predrag M. PY - 2017 UR - http://eteze.bg.ac.rs/application/showtheses?thesesId=5057 UR - https://fedorabg.bg.ac.rs/fedora/get/o:15788/bdef:Content/download UR - http://vbs.rs/scripts/cobiss?command=DISPLAY&base=70036&RID=49041935 UR - http://nardus.mpn.gov.rs/123456789/8300 UR - https://cherry.chem.bg.ac.rs/handle/123456789/2733 AB - Hiralni, polisupstituisani derivati pirolidina, dobijeni cikloadicionim reakcijamaazometinskih ilida, proučavani su kao organokatalizatori u Michael-ovoj reakciji aldehida/ketonai vinil-sulfona. Pod optimalnim reakcionim uslovima, u kojima se koristilo 10 mol % katalizatorau vlažnom metilen-hloridu prinosi reakcija su generalno bili dobri dok je enantioselektivnostvarirala dostižući 52 %.Razvijen je efikasan biokatalizator za asimetričnu Michael-ovu adiciju acetaldehida na β-nitrostiren na bazi celih ćelija koja eksprimira 4-oksalokrotonat tautomerazu (4-OT). Utvrđen jeoptimalan odnos supstrata i biokatalizatora. Kada je kao supstrat korišćen β-nitrostiren dobijenaje odlična enantioselektivnost (e.e. >99%) uz prinos reakcije do 60%. Biokatalizator je manjeefikasan sa p-hlor-, o-hlor- i p-fluor-β-nitrostirenom gde su dobijeni prinosi od 38%, 51%, 31% ie.e. 84%, 88%, 94%... AB - Chiral, polysubstituted pirrolydines derivatives, obtained via cycloaddition reactions ofazomethine ylides, were studied as organocatalysts in the Michael reaction of aldehydes/ketonesand vinylsulphones. Under optimised reaction conditions employing 10 mol % of the catalyst inwet CH2Cl2, the yields of the products were generally good while the enantioselectivity varied,reaching up to 52 %.A novel whole cell system based on recombinantly expressed 4-oxalocrotonatetautomerase (4-OT) was developed and shown to be an effective biocatalyst for the asymmetricMichael addition of acetaldehyde to β-nitrostyrenes. Optimal ratio of substrates and biocatalystwas determined. Excellent enantioselectivity (>99% ee) and product yields of up to 60% wereobtained with β-nitrostyrene substrate. The biocatalyst exhibited lower reaction rates with pchloro-,o-chloro- and p-fluoro-β-nitrostyrenes with product yields of 38%, 51%, 31% and eevalues of 84%, 88% and 94% respectively... PB - Универзитет у Београду, Хемијски факултет T2 - Универзитет у Београду T1 - Pirolidinski derivati u organokatalitičkim transformacijama UR - https://hdl.handle.net/21.15107/rcub_nardus_8300 ER -
@phdthesis{ author = "Jovanović, Predrag M.", year = "2017", abstract = "Hiralni, polisupstituisani derivati pirolidina, dobijeni cikloadicionim reakcijamaazometinskih ilida, proučavani su kao organokatalizatori u Michael-ovoj reakciji aldehida/ketonai vinil-sulfona. Pod optimalnim reakcionim uslovima, u kojima se koristilo 10 mol % katalizatorau vlažnom metilen-hloridu prinosi reakcija su generalno bili dobri dok je enantioselektivnostvarirala dostižući 52 %.Razvijen je efikasan biokatalizator za asimetričnu Michael-ovu adiciju acetaldehida na β-nitrostiren na bazi celih ćelija koja eksprimira 4-oksalokrotonat tautomerazu (4-OT). Utvrđen jeoptimalan odnos supstrata i biokatalizatora. Kada je kao supstrat korišćen β-nitrostiren dobijenaje odlična enantioselektivnost (e.e. >99%) uz prinos reakcije do 60%. Biokatalizator je manjeefikasan sa p-hlor-, o-hlor- i p-fluor-β-nitrostirenom gde su dobijeni prinosi od 38%, 51%, 31% ie.e. 84%, 88%, 94%..., Chiral, polysubstituted pirrolydines derivatives, obtained via cycloaddition reactions ofazomethine ylides, were studied as organocatalysts in the Michael reaction of aldehydes/ketonesand vinylsulphones. Under optimised reaction conditions employing 10 mol % of the catalyst inwet CH2Cl2, the yields of the products were generally good while the enantioselectivity varied,reaching up to 52 %.A novel whole cell system based on recombinantly expressed 4-oxalocrotonatetautomerase (4-OT) was developed and shown to be an effective biocatalyst for the asymmetricMichael addition of acetaldehyde to β-nitrostyrenes. Optimal ratio of substrates and biocatalystwas determined. Excellent enantioselectivity (>99% ee) and product yields of up to 60% wereobtained with β-nitrostyrene substrate. The biocatalyst exhibited lower reaction rates with pchloro-,o-chloro- and p-fluoro-β-nitrostyrenes with product yields of 38%, 51%, 31% and eevalues of 84%, 88% and 94% respectively...", publisher = "Универзитет у Београду, Хемијски факултет", journal = "Универзитет у Београду", title = "Pirolidinski derivati u organokatalitičkim transformacijama", url = "https://hdl.handle.net/21.15107/rcub_nardus_8300" }
Jovanović, P. M.. (2017). Pirolidinski derivati u organokatalitičkim transformacijama. in Универзитет у Београду Универзитет у Београду, Хемијски факултет.. https://hdl.handle.net/21.15107/rcub_nardus_8300
Jovanović PM. Pirolidinski derivati u organokatalitičkim transformacijama. in Универзитет у Београду. 2017;. https://hdl.handle.net/21.15107/rcub_nardus_8300 .
Jovanović, Predrag M., "Pirolidinski derivati u organokatalitičkim transformacijama" in Универзитет у Београду (2017), https://hdl.handle.net/21.15107/rcub_nardus_8300 .