Highly efficient total synthesis of Δ12-PGJ2, 15-deoxy-Δ12,14-PGJ2, and their analogues
Highly efficient total synthesis of Δ12-PGJ2, 15-deoxy-Δ12,14-PGJ2, and their analogues
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DOI：
10.1016/j.tet.2006.01.051
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发表时间：
2006-04-03
期刊：
影响因子：
2.1
通讯作者：
Kobayashi, Y
中科院分区：
文献类型：
--
作者：
Acharya, HP;Kobayashi, Y
钯催化4-环戊烯-1,3-二醇单乙酸酯（> 95% ee）的TBS醚与丙二酸甲酯衍生的阴离子和t-BuOK、LDA等碱进行了高效、可重复性的反应。得到的产物分离率为90%，经5步转化为具有α链的关键环戊烯酮。该烯酮与w链醛的醛缩反应得到醛缩加合物，衍生甲磺酸盐与Al2O3接触得到完整结构的交叉共轭二烯酮。最后，官能团处理有效地提供了Delta(12_)PGJ(2)。同样，合成了15-脱氧- δ (12,14_)PGJ(2), 5,6-乙炔类似物和5,6-二氢类似物。(c) 2006 Elsevier Ltd.版权所有。
Palladium-catalyzed reaction of TBS ether of 4-cyclopentene-1,3-diol monoacetate (> 95% ee) with an anion derived from methyl malonate and a base such as t-BuOK and LDA proceeded highly efficiently and reproducibly. The product obtained in > 90% isolated yield was transformed in five steps into the key cyclopentenone possessing the alpha-chain at the gamma position. Aldol reaction of this enone with the w-chain aldehyde afforded the aldol adduct, and exposure of the derived mesylate to Al2O3 furnished the cross-conjugated dienone of the full structure. Finally, functional group manipulation furnished Delta(12_)PGJ(2) efficiently. Similarly, 15-deoxy-Delta(12,14_)PGJ(2), 5,6-acetylene analogues, and a 5,6-dihydro analogue were synthesized. (c) 2006 Elsevier Ltd. All rights reserved.