Cyanide-catalyzed aldimine coupling was employed to synthesize compounds
with 1,2-ene-diamine and ñ-imine-amine structural motifs: 1,2,N,N'-
tetraphenyletheylene-1,2-diamine (13) and (+/-)-2,3-di-(2-hydroxyphenyl)-1,2-
dihydroquinoxaline (17), respectively. Single crystal X-ray diffraction provided solidstate
structures and density functional theory calculations were used to probe isomeric
preferences within this and the related hydroxy-ketone/ene-diol system. The enediamine
and imine-amine core structures were calculated to be essentially identical in
energy. However, additional effects-such as ÃÂ conjugation-in 13 render an enediamine
structure that is slightly more stable than the imine-amine tautomer (14). In
contrast, the intramolecular hydrogen bonding present in 17 significantly favors the
imine-amine isomer over the ene-diamine tautomer (18).
Aldimine coupling (AIC) is the nitrogen analogue of the benzoin condensation
and has been applied to dialdimines, providing the first examples of cyclizations effected
by cyanide-catalyzed AIC. Sodium cyanide promoted the facile, intramolecular
cyclization of several dialdimines in N,N-dimethylformamide, methanol, or
dichloromethane/water (phase-transfer conditions) yielding a variety of six-membered
heterocycles. Under aerobic conditions, an oxidative cyclization occurs to provide the
diimine heterocycle.
Cyanide-catalyzed aldimine coupling was employed as a new synthetic method
for oligomerization. Nine rigidly spaced dialdimines were oxidatively coupled under
aerobic conditions to yield conjugated oligoketimines and polyketimines with
unprecedented structure and molecular weight (DP = 2 - 23, ~700 -8200 g/mol). The ñ- diimine linkage was established based on IR spectroscopy, NMR spectroscopy, size
exclusion chromatography, and X-ray crystallographic characterization of the model
oxidized dimer of N-benzylidene-(p-phenoxy)-aniline. Cyclic voltammetry indicates ptype
electrical conductivity, suggesting they are promising candidates for plastic
electronic devices.
The cyanide-catalyzed benzoin condensation reaction of 4-substituted
benzaldehydes followed by oxidation to the diketone, and the Schiff Base condensation
of two equivalents of o-aminophenol provides 2,3-(4-X-phenyl)2-1,4-(2-
hydroxyphenyl)2-1,4-diazabutadiene. The ligand is given the moniker X-dabphol.
These ligands are readily metallated to form M-X-dabphol complexes. The copper
complexes catalytically fix CO2 with propylene oxide to yield propylene carbonate. DFT
studies along with a comparison with Hammet parameters help validate and elaborate on
the catalytic cycle and the catalytic results obtained. The nickel complex is competent
for olefin epoxidation. Synthesis, characterization, X-ray structure, DFT analysis, and
catalytic activity of the parent nickel dabphol complex are reported.
| Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/4987 |
| Date | 25 April 2007 |
| Creators | Reich, Blair Jesse Ellyn |
| Contributors | Miller, Stephen A |
| Publisher | Texas A&M University |
| Source Sets | Texas A and M University |
| Language | en_US |
| Detected Language | English |
| Type | Book, Thesis, Electronic Dissertation, text |
| Format | 5471568 bytes, electronic, application/pdf, born digital |
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