• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.824-829
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• 2002

New di-N-cyanomethylated tetraaza macrocycle 2.13-bis(cyanomethyl)-5.16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^7.12$]docosane $(L^2)$ has been prepared by the reaction of 3, 14-dimethyl-2,6,13,17-tetraazatricyclo $(L^1)$ with bromoacetonitrile. The square-planar complexes $[ML^2](ClO_4)_2(M=Ni(II)$ or Cu(II) can be prepared by the reaction of $L^2$ with the corresponding metal ion in acetonitrile. The cyanomethyl groups of $[ML^2](ClO_4)_2readily$ react with water to $yield[ML^3](ClO_4)_2$ containing pendant amide groups. The trans-octahedral complexes $[ML^4](ClO_4)_2$, in which two imidate ester groups are coordinated to the metal ion, can be also prepared by the reaction of $[ML^2](ClO_4)_2with$ methanol under mild conditions. The hydrolysis and alcoholysis reactions of $[ML^2](ClO_4)_2are$ promoted by the central metal ion, in spite of the fact that the cyanomethyl group is not involved in intramolecular coordination. The reactions are also promoted by a base such as triethylamine but are retarded by an $acid(HClO_4).Interestingly$, the imidate ester groups of $[ML^4]^2$ are unusually resistant to hydrolysis even in 0.1 M $HCIO_4$ or 0.1 M NaOH aqueous solution. Crystal structure of $[NiL^4](ClO_4)_2shows$ that the Ni-N (pendant imidate ester group) bond is rlatively strong; the Ni-N bond distance is shorter then the Ni-N(tertiary) distance and is similar to the Ni-N (secondary) distance.

• Bulletin of the Korean Chemical Society
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• v.24 no.12
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• pp.1723-1724
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• 2003

• Proceedings of the PSK Conference
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• 2003.10b
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• pp.182.3-183
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• 2003

(-)-Antofine is phenanthroindolizidine alkaloid being isolated from Cynanchum vincetoxicum. It has powerful cytotoxicity toward drug-sensitive KB-3-1 and multidrug resistant KB-V1 cancer cell line. We have successfully accomplished stereoselective total synthesis by using palladium catalyzed Stille coupling of l0-bromomethyl-2,3 ,6-trimethoxy-phenanthrene and (R)-(E)-4-(tributylstannanyl)but-3-en-2-o1, Overmann rearrangement of imidate, and RCM(ring-closing metathesis) for construction of pyrrolidine.