Divergent synthesis and chemical reactivity of bicyclic lactone fragments of complex rearranged spongian diterpenes.
Divergent synthesis and chemical reactivity of bicyclic lactone fragments of complex rearranged spongian diterpenes.
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复杂重排海绵二萜双环内酯片段的不同合成和化学反应性。
DOI：
10.1021/ja207727h
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发表时间：
2011-11-02
影响因子：
15
通讯作者：
Overman, Larry E.
中科院分区：
文献类型：
--
作者：
Schnermann, Martin J.;Beaudry, Christopher M.;Genung, Nathan E.;Canham, Stephen M.;Untiedt, Nicholas L.;Karanikolas, Breanne D. W.;Suetterlin, Christine;Overman, Larry E.
报道了在重排的海绵二萜中发现的两个高度氧化的双环内酯片段(8-取代的6-乙酰氧基-2，7-二氧二环[3.2.1]辛烷-3-酮和6-取代的7-乙酰氧基-2，8-二氧双环[3.3.0]辛烷-3-酮)的合成和化学反应活性的直接比较。描述了6-乙酰氧基-2，7-二氧双环[3.2.1]辛烷-3-酮环体系的首次合成的细节，包括对关键桥联环化反应的几种可能性的考察(方案2-5)。此外，公开了在C6处首次合成含有季碳取代基的7-乙酰氧基-2，8-二氧二环[3.3.0]辛酮(方案6)。还报道了这些重排的自体二萜的双环内酯类似物的化学反应活性和高尔基修饰性能。在酸性和碱性条件下，8-取代的2，7-二氧二环[3.2.1]辛酮转化为6-substituted-2，8-dioxabicyclo[3.3.0]octanones.此外，这些二恶二环内酯与溶菌酶的伯胺和赖氨酸侧链反应生成取代的吡咯，这种结合可能是这些化合物独特的生物学性质的原因。这些研究表明，无论是桥联的还是融合的系列，内酯羰基附近的乙酰氧基化都是需要的，才能在马法兰E的中心周围区域产生碎裂的高尔基膜。
The synthesis and direct comparison of the chemical reactivity of the two highly oxidized bicyclic lactone fragments found in rearranged spongian diterpenes (8-substituted 6-acetoxy-2,7-dioxabicyclo[3.2.1]octan-3-one and 6-substituted 7-acetoxy-2,8-dioxabicyclo[3.3.0]octan-3-one) are reported. Details of the first synthesis of the 6-acetoxy-2,7-dioxabicyclo[3.2.1]octan-3-one ring system, including an examination of several possibilities for the key bridging cyclization reaction, are described (Schemes 2–5). In addition, the first synthesis of 7-acetoxy-2,8-dioxabicyclo[3.3.0]octanones containing quaternary carbon substituents at C6 is disclosed (Scheme 6). Aspects of the chemical reactivity and Golgi-modifying properties of these bicyclic lactone analogs of rearranged spongian diterpenes are also reported. Under both acidic and basic conditions, 8-substituted 2,7-dioxabicyclo[3.2.1]octanones are converted to 6-substituted-2,8-dioxabicyclo[3.3.0]octanones. Moreover, these dioxabicyclic lactones react with primary amines and lysine side chains of lysozyme to form substituted pyrroles, a conjugation that could be responsible for the unique biological properties of these compounds. These studies demonstrate that acetoxylation adjacent to the lactone carbonyl group—in either the bridged or fused series—is required to produce fragmented Golgi membranes in the pericentriolar region that is characteristic of macfarlandin E.
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影响因子：
15
作者：
BROWN, HC;BREWSTER, JH;SHECHTER, H
通讯作者：
SHECHTER, H
影响因子：
3.5
作者：
Guizzunti, Gianni;Brady, Thomas P.;Theodorakis, Emmanuel A.
通讯作者：
Theodorakis, Emmanuel A.
影响因子：
1.8
作者：
COREY, EJ;BOAZ, NW
通讯作者：
BOAZ, NW
影响因子：
15
作者：
ARNETT, EM;HARRELSON, JA
通讯作者：
HARRELSON, JA
影响因子：
15
作者：
DESS, DB;MARTIN, JC
通讯作者：
MARTIN, JC