不斉ナノ空間の構築と不斉認識・不斉合成反応

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  • フセイ ナノ クウカン ノ コウチク ト フセイ ニンシキ フセイ ゴウセイ ハンノウ
  • Construction of Chiral Nano-Space toward Chiral Recognition and Asymmetric Reaction

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Abstract

Synthesis of axially chiral dicarboxylic acids with a rigid and straight structure was studied. The preparation of copper salt of this type of dicarboxylic acid was also studied. Optically active 2,2'-dihydroxy-1,1'-binaphthalene-4,4'-dicarboxylic acid 2a was prepared from the corresponding bromide 3 via cyanation followed by hydrolysis although the reaction proceeded in very low yield. We found that 2a could be effectively prepared from 3 via palladium complex-catalyzed vinylation followed by KMnO4 oxidation. Direct carboxylation of 3 via lithiation followed by the reaction with CO2 was unsuccessful because of the instability of the monolithiated intermediate. The synthesis of optically active allene-1,3-dicarboxylic acid 9 was investigated. The optical resolution of racemic 9 via the quinine salt was unsuccessful due to slow decomposition, therefore, diasteromeric resolution of (-)-menthyl ester was investigated. A copper (II) salt of racemic 2,2'-dihydroxy-1,1'-binaphthalene-3,3'-dicarboxylic acid 15 was prepared. X-ray crystallographic analysis of the single crystal of 15-Cu (II) showed a 2D infinite sheet structure, where each sheet was composed of only one of the enantiomers of 15. The crystal had micropores of 4.15 Å diameter, which well corresponded to the value obtained from the micropore size distribution measurement. Because of the micropore structure, the crystal showed a large surface area (BET: 642 m2g-1, Langmuire: 919 m2g-1).

■原 著■ 2007 年度神奈川大学総合理学研究所共同研究助成論文

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