Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Studies Towards Intramolecular Formal Iron-Catalyzed [4+2] Cycloaddition of Acetylenic Dienes

Fe(0) 촉매를 이용한 Acetylenic Dienes 의 분자내 [4+2] 고리화 첨가반응에 관한 연구

  • 변상용 (부산공업대학교 자연과학과)
  • Published : 19940100
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Abstract

The intramolecular formal iron-catalyzed [4+2] cycloaddition reaction of acetylenic dienes to produce bicyclic products has been investigated. These reactions proceeded, competing via intramolecular carbocyclization and bimolecular cycloaddition. However, the iron-catalyzed bicyclic carbocyclization of 4,4-dimethyl-3-(tert-butyldimethylsiloxy)-1-phenyl-6,8-decadien-1-yne(11) yielded exclusively bicyclic diene product(yield 78.1%). From this result, we found that the substrate containing a dimethyl substitutent at the 4,4-position helped to promote the intramolecular reaction, which is stable to the iron catalyzed conditions.

Fe(0)촉매하에서 이중고리 생성물이 얻어지는 acetylenic diene을 반응시켜 분자내 [4+2]고리화 첨가반응을 조사하였다. 위 반응은 이분자 첨가반응과 분자내 탄소 고리화 반응이 경쟁적으로 진행된다고 알려져 있다. 그러나 Fe(0)촉매하에서 4,4-dimethyl-3-(tert-butyldimethylsiloxy)-1-phenyl-6,8-decadien-1-yne(11)의 고리화 반응은 단지 이중고리 생성물만이 얻어졌다(수득율 78.1%). 이 결과에서 dienyne의 4,4-위치에 치환된 dimethyl기가 Fe(0)촉매하의 고리화 반응조건에 안정함으로 인하여 분자내 고리화 반응이 촉진되는 것으로 생각된다.

Keywords

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