Cooperative Catalysis in Aldoltype Reactions: A DFT Study

1
Cooperative Catalysis in Aldol-type Reactions A
DFT Study
Ivan Konstantinov Northwestern University Mentor
Prof. Linda J. Broadbelt
Research Goal Examine the cooperative effect in
small bifunctional molecules and surfaces with
weak-acid/base sites on the catalysis of
aldol-type reactions. Payoff Create
structure-reactivity relationship that will allow
for the creation of improved catalysts.
Figure 1. Structure of hydroxylated amorphous
alumina.
Figure 2. Proposed reaction pathways for the
L-proline catalyzed ?-aminoxylation of aldehydes.

• Approach
• Use DFT to map the reaction coordinates in
  homogenous (small molecules as catalysts, Figure
  2) and heterogeneous conditions (catalytic
  surfaces, Figure 1).
• Create microkinetic models that allow for
  determination of the rate-limiting steps and
  comparison with experimental data.

• Results
• L-proline has two active sites (an amino group
  and a carboxyl moiety) which act in tandem to
  guide the reaction through an energetically more
  efficient pathway that involves the formation of
  an enamine intermediate as compared to
  traditional acid/base catalyzed reactions.
• Our current investigation of amorphous
  hydroxylated alumina shows that it is an
  attractive choice for a catalytic surface due to
  the presence of mildly acidic hydroxyl groups.