Unprecedented cobalt-catalyzed isomerization reactions to single skipped 2,4,7-trienes applied in the synthesis of urushiol.
Unprecedented cobalt-catalyzed isomerization reactions to single skipped 2,4,7-trienes applied in the synthesis of urushiol.
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DOI：
10.1002/asia.201402323
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发表时间：
2014-09
期刊：
影响因子：
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通讯作者：
Anastasia Schmidt;G. Hilt
中科院分区：
文献类型：
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作者：
Anastasia Schmidt;G. Hilt
对于侧链中具有额外双键的非常具有挑战性的底物，实现了钴催化的1，3-二烯异构化为2 Z，4 E-二烯。未观察到异构化为共轭3，5，7-三烯衍生物，这与许多其它异构化催化剂的观察结果形成鲜明对比。因此，研究了侧链上具有敏感的2 Z，4 E，7Z-三烯亚基的天然产物漆酚的合成。O-保护的漆酚衍生物选择性地生成，而不异构化为共轭3，5，7-三烯或在7位的双键的Z/E-异构化。
The cobalt-catalyzed isomerization of 1,3-dienes to 2Z,4E-dienes was realized for the very challenging substrates with an additional double bond in the side chain. An isomerization to the conjugated 3,5,7-triene derivative was not observed, which is in stark contrast to observations with many other isomerization catalysts. Accordingly, the synthesis of the natural product urushiol, which has a sensitive 2Z,4E,7Z-triene subunit in the side chain, was investigated. The O-protected urushiol derivative was generated selectively without isomerization to the conjugated 3,5,7-triene or Z/E-isomerization of the double bond at position 7.