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).
内容記述
■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
雑誌名
Science Journal of Kanagawa University
巻
19
ページ
27 - 32
発行年
2008-06-30
ISSN
1880-0483
書誌レコードID
AA12068302
著者版フラグ
publisher
その他の言語のタイトル
Construction of Chiral Nano-Space toward Chiral Recognition and Asymmetric Reaction
不斉ナノ空間の構築と不斉認識・不斉合成反応
06 19 27-32.pdf
(3.22MB)
