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Anwar.Asymmetric synthesis

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Anwar.Asymmetric synthesis

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Anwar.Asymmetric synthesis

  1. 1. Asymmetric synthesis Dr. Shaikh A. R
  2. 2. • Asymmetric catalytic reduction:Asymmetric catalytic reduction is the use of various chiral catalysts to reduce a pro-chiral organic compound to obtain a chiral product. This is one of the several techniques used in chiral synthesis.e.g. H (g) O O 2 OH O RuCl2 [(R)-BINAP] R OMe MeOH R OMe BINAP=2,2-bis(diphenylphosphino)-1,1-binaphthylThe Noyori asymmetric hydrogenation is a chemical reaction described as anasymmetric reduction of β-keto esters.Example in drug synthesis: Synthesis of Naproxen
  3. 3. Synthesis of Naproxen:
  4. 4. • Asymmetric catalytic oxidation:• Is a technique of oxidising various substrate to give an enantiopure product using a catalyst.• Reactions:• Jacobsen epoxidation of alkenes using manganese- salen complex and NaOCl• Sharpless epoxidation of allyl alcohols using titanium isopropoxide, diethyl tartrate, and t-butyl hydroxyperoxide• Sharpless asymmetric dihydroxylation of alkenes using dihydroquinine or dihydroquinidine ligands on an osmium metal center• Shi epoxidation of alkenes using oxone and a fructose- derived chiral catalyst• Sulfonyloxaziridine enolate oxidation
  5. 5. • Sharpless epoxidation: Example in drug synthesis: Synthesis of Propranolol
  6. 6. • Synthesis of propranolol: HO SiCH3 SiCH3 H OH H
  7. 7. • Sharpless epoxidation: Example in drug synthesis: Synthesis of Propranolol
  8. 8. OHO SiCH3 HO SiCH3 ArONa ONa CH3 H3C NH NH 2 H O H3C CH3 OH 4 SCH SiCH3 OH O Tetra-n-butylammonium fluoride SCH3 O Na Bu4NF iprNH2
  9. 9. Synthesis of penicillamin NaOH or Penicillinase - H+ :OH R NH S CH3 CH3 H + OR N OH ..- N: - + NH CH2 CH HS CH3 COOH + O OH OH O CH3 NH ..- CH Decarboxylation H COOH R NH C CH S CH3 H2 O O N CH3 OH H Hydrolysis
  10. 10. Synthesis of penicillamin H OHR N CH2 CH HS CH3 + OH O CH3 NH ..- CH H COOH
  11. 11. Synthesis of Aspartame MeOOC H O COOH N NH2 H H O MeOOC HOOC H C NH C 3 CH COOH NH2 H
  12. 12. Catalytic asymmetric hydrogenation COOH (1)-(R,R)-PNNP-Rh (I) (Cat) NHAC Me COOH (1)-H +. MeOH(z)-2-acetamido-3-phenylacrylic acid H NHAC S-phenylalanine methyl ester (97 %) Or (s)- methyl 2-acetamido-3-phenylpropanoate COOMe MeOOC H NH AC .. O + H .. NH COOH AC H NH2 O O HO COOH - CH3+C CH3 COOH H NH2 :OH Aspartic acid
  13. 13. Synthesis of ethambutol (S,S) OH HMe N N Me H HO COOH NH2 MeS L-Methionine
  14. 14. COOH a. MeOH, ACCl NH2MeS b. ClCOCOCl (0.5 Aq.), Pyridine, CHCl2 COOMe H SMe N H N MeS O O COOMe Oxalyl diamide
  15. 15. COOH COOH .. NH .. 2 H2N .. NH COOHMeS . .. MeS COOH + NH2 SMe C C C Cl - MeS Cl: Cl Cl O O O O
  16. 16. COOMe COOMe COOMeCOOMe COOMe COOMe Raney Ni, MeOH, H2O NH HN HN NH NH HNMeS Desulfuration Me O O O O Me O O SMe MeS COOMe O Me H SMe N N Me H O COOMe Penultimate Exhaustive reduction LiAlH4, THF COO H O Me H Me N N Me H O COOH Me Ethambutol
  17. 17. Synthesis of Atenolol O O O O N S O O N OH H OH S-Glycidylnosylate O O O N OH H CH2CONH22-(4-Hydroxyphenyl)acetamide CH2CONH2 CH2CONH2 O O O O N S Atenolol OH
  18. 18. O O O O N S O OOCH2CONH2 O O O CH S. 2 O N -.O .. O + H..O + CH2CONH2
  19. 19. Synthesis of Atenolol O O O O N S O O O O N O OH H O O OH S-Glycidylnosylate + O N S OH CH2CONH2 CH2CONH2 H3C2-(4-Hydroxyphenyl)acetamide NH2 Isopropyl amine H3C O N OH H Atenolol CH2CONH2
  20. 20. CH3 + .N .. .+ CH3 CH2 H . .O O- O N OH HCH2CONH2 CH2CONH2

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