Reaction – Nucleophilic acyl substitution

1. Reaction –Nucleophilicacyl substitution Yixun Xing

2. Reaction

3. Reaction Mechanism

4. Reaction Mechanism • Nucleophilic Substitution— A fundamental class of substitution reaction in which an "electron rich" nucleophile selectively bonds with or attacks the positive or partially positive charge of an atom attached to a group or atom called the leaving group; the positive or partially positive atom is referred to as an electrophile.

5. Nucleophilicacyl substitution— Upon attack of the nucleophile at the carbonyl group, a tetrahedral intermediate is formed with the nucleophile, the leaving group and the oxygen anion attached to the central carbon atom. The alkoxy group can now revert back to the carbonyl group and at the same time expel the leaving group.

6. Homo:MO28 Energy: -10.89670evLumo:MO29 Energy: 5.31218 ev

7. Homo: MO 46 Energy: -11.52918evLumo:MO47 Energy: 2.89761ev

8. Energy Gap • E(LUMO) -E (HOMO) • = 2.89761ev-(-10.89670ev) =13.79431ev

9. Distance: 4.0 Å Distance: 3.5 Å

10. Distance: 3.0 Å Distance: 2.5 Å

11. Distance: 2.0 Å Distance: 1.8 Å

12. Distance: 1.6 Å Distance: 1.4 Å

13. Distance: 1.2 Å Distance: 1.0 Å

15. Product

16. Homo: MO 56 Energy: -11.16780ev Lumo: MO57 Energy: 2.76860ev