A total synthesis of the styryllactone (+)-goniodiol from naphthalene.
A total synthesis of the styryllactone (+)-goniodiol from naphthalene.
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DOI：
10.1071/ch02242
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发表时间：
2003-06
影响因子：
1.1
通讯作者：
M. Banwell;M. J. Coster;A. Edwards;Ochitha P. Karunaratne;Jason A. Smith;L. L. Welling-L.;A. Willis
中科院分区：
文献类型：
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作者：
M. Banwell;M. J. Coster;A. Edwards;Ochitha P. Karunaratne;Jason A. Smith;L. L. Welling-L.;A. Willis
从萘的微生物氧化得到的顺式二氢邻苯二酚（2）出发，经十二步反应合成了具有细胞毒性的天然产物（+）-戈碘酚（1）。化合物（2）的酯化包括初始氧化裂解为二醛（7），然后还原得到二醇（12）。化合物（12）转化为缩醛（17）阿利亚需要苯甲醇部分的选择性氧化，然后对所得醛进行金属催化脱羰。化合物（17）在高氯酸锂存在下与烯丙基三丁基锡烷烯丙基化，得到约1.5 - 1.5摩尔的化合物（17）。2.7 1：1的醇（18）和（19）的混合物，在标准条件下将其各自转化成相应的丙烯酸酯。这些酯衍生物用Grubbs的第一代催化剂进行闭环复分解（RCM）反应，得到预期的内酯（22）和（23）。然后酸催化除去化合物（22）中的丙酮化物保护基，得到（+）-戈碘醇（1），而同类物（23）的类似脱保护得到6-表-（+）-戈碘醇（24）。
The cytotoxic natural product (+)-goniodiol (1) has been prepared in twelve steps from the enantiomerically pure cis-dihydrocatechol (2), which is readily obtained by microbial oxidation of naphthalene. Elaboration of compound (2) involves an initial oxidative cleavage to dialdehyde (7) followed by reduction to give diol (12). Conversion of compound (12) into acetal (17) required, inter alia, selective oxidation of the benzylic alcohol moiety followed by a metal-catalyzed decarbonylation of the resulting aldehyde. Allylation of compound (17) with allyltributylstannane in the presence of lithium perchlorate gave a ca. 2.7 : 1 mixture of alcohols (18) and (19), each of which was converted into the corresponding acrylate under standard conditions. Subjection of these ester derivatives to a ring-closing metathesis (RCM) reaction with Grubbs' first-generation catalyst gave the anticipated lactones (22) and (23). Acid-catalyzed removal of the acetonide protecting group within compound (22) then afforded (+)-goniodiol (1), while analogous deprotection of congener (23) afforded 6-epi-(+)-goniodiol (24).