Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Synthesis of 6-Hydroxyalkylidenepenicillanates

6-히드록시알킬리덴페니실란산 염의 합성

  • Lee, Jung Hwan (Department of Chemistry, Seoul National University) ;
  • Ko, Jae Young (Department of Chemistry, Seoul National University) ;
  • Seo, Kyung Jae (Department of Chemistry, Seoul National University) ;
  • Goo, Yang Mo (Department of Pharmacy, Seoul National University) ;
  • Lee, Youn Young (Department of Chemistry, Seoul National University)
  • 이중환 (서울대학교 자연과학대학 화학과) ;
  • 고재영 (서울대학교 자연과학대학 화학과) ;
  • 서경재 (서울대학교 자연과학대학 화학과) ;
  • 구양모 (서울대학교 약학대학 약학과) ;
  • 이윤영 (서울대학교 자연과학대학 화학과)
  • Published : 19990800
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Abstract

Allyl (5R)-(Z)- and (5R)-(E)-6-[(2S)-2,3-isopropylidenedioxypropylidene]Penicillanate(10a and 10b) were prepared from allyl (5R)-dibromopenicillanate(6) via a sequence of reactions involving condensation with 2,3-O-isopropylidene-D-glyceraldehyde, reduction with $Zn-NH_4OAc$, and Mitsunobu elimination. Deprotection of isopropylidene and allyl groups of 10a gave potassium (5R)-(Z)-6-[(2S)-2,3-dihydroxypropylidene]penicillanate(4). However, deprotection of isopropylidene group of 10b afforded ${\alpha},\;{\beta}$-unsaturated-lactone(12). Allyl (5R)-(Z)- and (5R)-(E)-6-[(2S)-2-(t-butyldimethlsilyloxy)propylidene]penicillanate(18a and 18b) were prepared from ally (5R)-dibromopenicillanate(6) via a sequence of reactions involving condensation with (2S)-2-(t-butyldimethylsilyloxy)propanal(15), reduction with $Zn-NH_4OAc$ and Mitsunobu elimination or mesylation-elimination. Deprotection of t-butyldimethylsilyl and allyl groups of 18a and 18b gave potassium (5R)-(Z)- and (5R)-(E)-6-[(2S)-2-hydroxypropylidene]penicillanate(5a and 5b), respectively.

Allyl (5R)-dibromopenicillanate(6)의 2,3-O-isopropylidene-D-glyceraldehyde와의 축합, $Zn-NH_4OAc$에 의한 환원 및 Mitsunobu 제거반응의 일련의 과정을 거처서 allyl (5R)-(Z) 및 (5R)-(E)-6-[(2S)-2,3-isopropylidenedioxypropylidene]penicillanate(10a 및 10b)를 합성하였다. 화합물10a의 이소프로필리덴 및 알릴 보호기를 제거하여 potassium (5R)-(Z)-6-[(2S)-2,3-dihydroxypropylidene]penicilla-nate(4)를 얻었다. 그러나 화합물 10b의 이소프로필리덴 보호기를 제거한 결과 ${\alpha},\;{\beta}$-unsaturated-lactone(12)이 얻어짐을 확인하였다. Allyl(5R)-6,6-dibromopenicillanate(6)의 (2S)-2-(t-butyldimethyl-silyloxy)propanal(15)과의 축합, $Zn-NH_4OAc$에 의한 환원 및 Mitsunobu 제거반응 또는 메실화-제거반응의 일련의 과정을 거처서 allyl (5R)-(Z)- 및 (5R)-(E)-6-[(2S)-2-(t-butyldimethylsilyloxy)propylidene]-penicillanate(18a 및 18b)를 합성하였다. 화합물 18a 및 18b의 t-부틸디메틸실릴 및 알릴 보호기를 제거하여 potassium (5R)-(Z)- 및 (5R)-(E)-6-[(2S)-2-hydroxypropylidene]penillanate(5a 및 5b)를 얻었다.

Keywords

References

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