Applied Chemistry for Engineering (공업화학)

The Korean Society of Industrial and Engineering Chemistry (한국공업화학회)
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Synthesis of Optically Active Monoesters via Kinetic Resolution by Chiral Co (Salen) Complex Immobilized on Mesoporous BEA

메조세공 BEA에 고정화된 키랄 Co살렌 착체의 동적분할을 통한 고광학순도의 키랄 모노에스테르 합성

  • Received : 2014.08.06
  • Accepted : 2014.10.30
  • Published : 2015.04.10
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Abstract

BEA-zeolite was modified by alkaline solution to introduce mesoporosity in the crystals and the homogeneous chiral Co(III) salen was immobilized in the mesopores. The dinuclear chiral Co(salen)-$GaCl_3$ catalyst immobilized on mesoporous BEA-zeolite showed high activity for the regioselective ring opening of terminal epoxides by carboxylic acids. Various chiral monoester derivatives could be synthesized with moderate enantioselectivity (47~69 ee%) from racemic epoxides through above reaction. When the chiral (S)-ECH was used as a reactant, it was efficiently resolved by carboxylic acid with a high enantioselectivity in the presence of heterogenized chiral salen catalyst, and the ring opened product afforded optically pure monoester epoxide (R)-GB (up to 98 ee%) through the ring closing in the basic solution by elimination of HCl. The heterogeneous catalyst could be fabricated easily, and the catalytic activity was retained for several times reuse without any further regeneration step.

BEA형 제올라이트를 알칼리용액으로 처리하여 결정구조 내에 메조세공이 형성되도록 제조하고, 세공 내에 균일계 키랄 Co(III) 살렌을 고정화시켰다. 메조세공 BEA-제올라이트에 고정화된 이핵형 Co-$GaCl_3$ 살렌 촉매는 말단 에폭사이드의 산소고리를 카르복실산으로 여는 키랄 반응에 대하여 높은 활성을 나타내었다. 이 반응을 통하여 라세믹 에폭사이드로부터 다양한 모노 에스테르 유도체를 중간 정도의 광학선택도(47~69 ee%)로 합성할 수 있었다. 키랄(S)-ECH를 반응물로 사용하면, 이들은 키랄 살렌 촉매 존재하에서 카르복시 산에 의하여 에폭사이드의 링이 광학선택적으로 열리며, 생성된 화합물을 염기용액에서 탈염산 처리하면 다시 에폭사이드 링이 형성되면서 광학순도가 매우 높은 모노에스터 에폭사이드 (R)-GB (98 ee% 이상)가 얻어졌다. 고정화촉매는 매우 용이하게 제조될 수 있었으며, 특별한 재생처리 없이 여러번 재사용하여도 촉매의 활성이 유지되었다.

Keywords

References

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