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Chem-806 PowerPoint Presentation

Chem-806

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Chem-806

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  1. Chem-806 Other Examples: COSY and NOESY

  2. CH close to D CH close to d D d Dd Dd D d R = Distinguish structures Rotation around Amide bound: 2 isopropyl shifts

  3. Distinguish structures D d Me-Ph Dd iPr(Me) iPr(Me) iPr(CH) iPr(CH) CHCl3 CH2Cl2

  4. a c b Distinguish structures c a b b a c CH2Cl2 X

  5. a c/b CH CH Distinguish structures : COSY iPr(Me) Me CH CH2 iPr CH(iPr) c b b a a a a CH2 b c

  6. a c/b NOESY: Phasing (small molecule) iPr(Me) Me CH CH2 Diagonal in Blue : Negative Cross peak in Blue : Negative indicate Chemical exchange Cross peak in Black : Positive indicate NOE effect (distance) exchange 5.03 exchange 3.47

  7. CH2 c a Distinguish structures : NOESY CH c/b a CH2 Strong R-group c a weak

  8. Me CH a CH NOESY slices a CH-iPr c CH2 weak CH-iPr iPr-Me Me c a b c CH c/b a CH2 CH-iPr CH-iPr

  9. CH-iPr NOESY slice: Chem. Exchange + NOE iPr-Me CH c CH-iPr iPr-Me CH Me a R = CH2 b c CH c/b a CH2 CH-iPr CH-iPr

  10. Another example a R= b c c a b

  11. c a b CH3 CH3 COSY CH CH2 CH CH2 a CH2 b c R= a

  12. NOESY Diagonal in Blue : Negative Cross peak in Blue : Negative Chemical exchange Cross peak in Black : Positive NOE effect (distance) Exchange

  13. c a CH3 CH3 NOESY CH c CH2 a b CH CH2 a CH2 b c CH2 R-group R c a weak

  14. a c CH2 CH3 CH NOESY Slices a CH2 b NOE c Exchange Weak CH2 CH3 CH3 CH CH2 c a CH2 b

  15. Me C’ ▲ a B’ b ▲’ A’ c ▲ ▲ ● ● ● ● ● ● Third example TMS Et ● A’/a TMS CH3 CH2

  16. a2 a1 a2 a1 Me1 Me2 Third example: COSY Me Et A’/a? ▲ ▲ C’ ▲ a B’ ● b ▲’ A’ c bB aA TMS ▲2 ▲1

  17. ● ● CH3 NOESY to identify Me TMS A’ a1 ▲’ Et a2 ▲1 ▲2 C’ ● ▲ a B’ ● a2 ▲2 b ▲’ A’ c TMS TMS side: a2 = A’, ▲2 = ▲’ Ethyl side: a1 =a, ▲1 = ▲ a1 ▲1

  18. COSY: Identify aromatic protons b/c Et A’ a C’ ▲ a B’ C’ B’ ● b ▲’ A’ c TMS

  19. A’ a NOESY: Identify aromatic protons Et C’ ▲ a Me1 B’ ● b ▲’ A’ c Me2 TMS Me b B’ Me1 Me2

  20. NOESY to identify stereochemistry Me TMS a Et A’ ▲ ▲’ C’ ● ● ▲ a B’ ● b ▲’ A’ c TMS Study interaction of CH(▲ and ▲’) with aromatic protons and with CH2

  21. b/c A’ a B’ C’ Me ▲’ c A’ (TMS)▲’ (Et)▲ NOESY expansion: Geometry of CH Et C’ ▲ a B’ ● b ▲’ A’ c TMS R a c A’ a C’