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| NIRE Annual Report | 
| 1998 |
Synthesis of Novel Ligands to Mimic Copper-containing EnzymesExcited State Chemistry DivisionAtmospheric Environmental Protection Department |
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Objectives
Metal-containing enzymes can capture low-reactive gas molecules such as nitrous oxide and carbon dioxide. The objective of this study is to synthesize enzyme-like host molecules. We synthesized novel ligands to mimic an enzyme containing a multi-copper cluster part.
Results
cis,cis-1,3,5-Triformyl-1,
3,5-trimethylcyclohexane (1) as the raw material of new ligands was obtained in three steps from cis,cis-1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid. Compound 1 has not been known because of its instability. The reaction of 1 with equimolar amounts of primary amines in CHCl3 at room temperature for 1-3 h yielded 3-aza-5,12-dioxawurtzitanes (3-aza-5,12-dioxatetracyclo[5.3.1.12,6.04,9]dodecanes) (2). Fig.1 shows a structure of 2. Azadioxawurtzitanes 2 are the first examples containing two different heteroatoms on the wurtzite structure. The reaction of 1 with large excess of histamine in CHCl3 at room temperature gave triazawurtzitane 3. Mechanistic study suggests that the thermal stabilities of 2 and 3 can be ascribed to their ipso methyl groups.
Selected Publications
1) Synthesis and cyclization reaction of cis,cis-1,3,5-triformyl-1,3,5-trimethylcyclohexane, J. Org. Chem., 62, 1173 (1997). 2) Synthesis of mixed heteroatom wurtzitanes, J. Chem. Soc., Perkin Trans. 1, in press.
