| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2005: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2004: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2003: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Research Abstract |
It has been establisehd that Zn^<2+> complex of a 12-membered macrocyclic tetraamine (Zn^<2+>-cyclen) recognize a variety of anions to form a stable complexes with these anions in aqueous solution at neutral pH. Previously, we have reported that tris(Zn^<2+>-cyclen) (Zn_3L^1) and trianion of trithiocyanuric acid (TCA^<3->) assembly in a 4:4 ratio to form a cuboctahedral supramolecular capsule in aqueous solution. This supermolecule possesses an inner cavity, in which size-matched and hydrophobic guest molecules are encapsulated. One of outstanding properties of the cuboctrahedron was its chirality, while both building blocks (Zn3L and TCA) contain no chiral center.
The purpose of this project is to design and synthesize an optically active cuboctahedron by self-assembly of a chiral derivative of Zn^<2+>-cyclen, Zn^<2+>-(S,S,S,S)-2,5,8-11-tetramethylcyclen, ((S,S,S,S)-ZnL^2), with TCA.
(S,S,S,S)-ZnL^2 was synthesized as follows : 1)L-alanine was reduced with LiAlH_4 to yield L-alaninol, 2)L-alaninol was reacted with benzaldehyde inthe presence of NaBH_4 to give N-benzyl-L-alaninol, 3)N-benzyl-L-alaninol was reacted with DEAD and yielded an aziridine derivative, which was reacted with TsOH to give a 12-membered macrocycle. This optically active 12-membered macrocycle, (S,S,S,S)-2,5,8-11-tetramethylcyclen, was reacted with (Boc)_2O to afford (S,S,S,S)-2,5,8-11-tetramethyl-1,4,7-tris(tert-butyloxycarbonyl)cyclen.
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