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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 43, Number 4
JKCSEZ 43(4)
August 20, 1999 

 
Title
Synthesis of 6-Hydroxyalkylidenepenicillanates

6-히드록시알킬리덴페니실란산 염의 합성
Author
Jung Hwan Lee, Jae Young Ko, Kyung Jae Seo, Yang MO Goo, Youn Young Lee

이정환, 고재영, 서경재, 구양모, 이윤영
Keywords
Abstract
Allyl (5R)-dibromopenicillanate(6)의 2,3-O-isopropylidene-D-glyceraldehyde와의 축합, Zn-NH4OAc에 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 1Ob의 이소프로필리덴 보호기를 제거한 결과 α,β-unsaturated-Υ-lactone(12)이 얻어짐을 확인하였다. Allyl(5R)-6,6-dibromopenicillanate(6)의 (2S)-2-(t-butyldimethyl-silyloxy)propanal(15)과의 축합, Zn-NH4OAc에 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.

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-NH4OAc, and Mitsunobuelimination. Deprotection of isopropylidene and allyl groups of l0a gave potassium (5R)-(Z)-6-[(2S)-2,3-dihydroxypropylidene]penicillanate(4) However, deprotection of isopropylidene group of 1Ob afforded α,β-unsaturated-Υ-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-NH4OAc 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.

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447 - 455
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