Stereoselective Syntheses of trans-Anhydromevalonic Acid and <i>trans</i>-Anhydromevalonyl Group-Containing Natural Products
Stereoselective Syntheses of trans-Anhydromevalonic Acid and <i>trans</i>-Anhydromevalonyl Group-Containing Natural Products
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反式脱水甲羟戊酸和含反式脱水甲羟戊酸天然产物的立体选择性合成
DOI：
10.1021/acs.jnatprod.1c01176
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发表时间：
2022
影响因子：
5.1
通讯作者：
Shinada Tetsuro
中科院分区：
文献类型：
--
作者：
Nakayama Atsushi;Yasuno Yoko;Yamamoto Yuki;Saito Kai;Kitsuwa Kohei;Okamura Hironori;Shinada Tetsuro
以反式脱水甲羟戊酸（tAHMA）酯为关键中间体，实现了反式脱水甲羟戊酸（tAHMA）和含tAHM基团的天然产物（pestalotiopin A、pestalotiopamide C、pestalotiopamide D、farinomalein E、eleutherazine B和β-环二肽A）的集体全合成。为此，通过3-氧代-5-（（三异丙基甲硅烷基）氧基）戊酸叔丁酯的Z-乙烯基甲苯磺酰化，然后与Me 2 Zn的Negishi交叉偶联反应，新制备了tAHMA叔丁酯。通过酯化或酰胺化将tAHMA酯转化为目标天然产物。合成产物和天然产物的光谱数据的比较证实了天然产物中tAHM部分的E-构型。
Collective total syntheses oftrans-anhydromevalonic acid (tAHMA) andtrans-anhydromevalonyl (tAHM) group-containing natural products (pestalotiopin A, pestalotiopamide C, pestalotiopamide D, farinomalein E, eleutherazine B, and trichocyclodipeptide A) were achieved using tAHMA esters as key intermediates. To this end, tAHMAtert-butyl ester was newly prepared byZ-vinyltosylation oftert-butyl 3-oxo-5-((triisopropylsilyl)oxy)pentanoate followed by the Negishi cross-coupling reaction with Me2Zn. tAHMA esters were converted to the target natural products via esterification or amidation. Comparison of the spectroscopic data of synthetic and natural products confirmed theE-configuration of the tAHM moieties in the natural products.