Synthesis of organic compounds for two-photon initiated polymerization and molecular recognition
Abstract
In section I, three-dimensional polymeric objects were fabricated using
two-photon initiated polymerization (TPIP) with a two-photon absorbing
chromophore and an acrylate resin. The feasibility of fabricating polymeric
features on the nanoscale was explored using an enhanced field generated at the
apex of a gold tip as the excitation source, as used in near-field excitation (NFE).
In section II, C3-symmetric chiral receptors were used to direct enantioselective
enolate alkylation. A series of host compounds was synthesized and 1:1 host to
enolate binding was observed by 1
H NMR titration experiments. A moderate
increase in the enantioselectivity of the alkylation of 2-acetylcyclohexanone was
observed in the presence of host 2.22. Also in section II, the use of enolate
stabilization via charge-pairing was investigated for the reduction of the pKa of 2-
acetylcyclopentanone. In the presence of host 3.12, the pKa of 2-
acetylcyclopentanone was reduced by 10 pKa units. In comparison with the 2.9
pKa unit shift observed with host 3.11, this result suggests that charge-pairing is
more effective in stabilizing enolates in enzyme active sites than traditional
hydrogen bonding.
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