Chemoenzymatic total syntheses of the linear triquinane-type natural products (+)-hirsutic acid and (-)-complicatic acid from toluene
Chemoenzymatic total syntheses of the linear triquinane-type natural products (+)-hirsutic acid and (-)-complicatic acid from toluene
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DOI：
10.1016/j.tet.2007.03.073
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发表时间：
2007-07-09
期刊：
影响因子：
2.1
通讯作者：
Willis, Anthony C.
中科院分区：
文献类型：
--
作者：
Banwell, Martin G.;Austin, Kerrie A. B.;Willis, Anthony C.
以顺-1，2-二氢邻苯二酚7为原料，实现了标题天然产物1和2的全合成。利用过量表达甲苯双加氧酶(TDO)的基因工程微生物大肠杆菌JM109(PDTG601)，通过甲苯的全细胞生物转化，很容易获得大量的、对映体纯的化合物7。这些合成包括三个关键步骤，第一步是双烯8与环戊酮在高压下的Diels-Alder环加成反应，得到加合物9；第二步是光化学促进的二环[2.2.2]辛烯酮衍生物18的氧杂二聚甲烷重排反应，得到20；第三步是最后一个化合物的还原裂解，得到线性三喹烷22。按照常规和/或既定程序将化合物22拟订为具体目标1和2。对化合物10-13、15、18、24和34进行了单晶X射线分析。(C)2007爱思唯尔有限公司。保留所有权利。
Total syntheses of title natural products, 1 and 2, have been achieved using the cis-1,2-dihydrocatechol 7 as starting material. Compound 7 is readily obtained in large quantity and enantiomerically pure form through the whole-cell biotransformation of toluene using the genetically engineered micro-organism Escherichia coli JM109 (pDTG601) that over-expresses the enzyme toluene dioxygenase (TDO). Three key chemical steps were employed in these syntheses, the first of which was a high-pressure- promoted Diels-Alder cycloaddition reaction between diene 8 and cyclopentenone to give adduct 9. The second key step was the photochemically promoted oxa-di-pi-methane rearrangement of the bicyclo[2.2.2] octenone derivative, 18, of 9 to give 20 while the third key step was the reductive cleavage of the last compound so as to afford the linear triquinane 22. Elaboration of compound 22 to targets 1 and 2 followed conventional and/or established procedures. Single-crystal X-ray analyses were carried out on compounds 10-13, 15, 18, 24, and 34. (c) 2007 Elsevier Ltd. All rights reserved.