Gold-Catalyzed Tandem Cycloisomerization/Cope Rearrangement: An Efficient Access to the Hydroazulenic Motif
Gold-Catalyzed Tandem Cycloisomerization/Cope Rearrangement: An Efficient Access to the Hydroazulenic Motif
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DOI：
10.1002/anie.201304497
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发表时间：
2013-08-19
影响因子：
16.6
通讯作者：
Gagosz, Fabien
中科院分区：
文献类型：
--
作者：
Cao, Ziping;Gagosz, Fabien
考虑到大量生物相关的天然产物在其(多环)结构中具有该基本单元的特征，允许构建七元碳环的合成方法的发展在有机合成中是最重要的。[1]在迄今报道的不同方法中，过渡金属催化的[5+2]和[4+3]环加成反应肯定被认为是最有合成价值的。[2，3]它们确实允许广泛、收敛和有效地获得各种七元环，当以分子内的方式进行时，有可能迅速且显著地增加结构复杂性。成熟且可能是最有效的生成1，4-环庚二烯基团1例如依赖于Rh(I)或Ru(II)催化的乙烯基环丙烷和炔之间的[5+2]环加成反应，[2a-d]或Rh(II)催化的二烯和乙烯基重氮衍生物之间的[4+3]环加成反应[式(1)]。[2e]最近，亲电的铂(II)和金(I)物种也显示出它们通过烯丙烯和二烯之间的[4+3]环加成反应生成1的催化潜力[式(1)]。
The development of synthetic methods allowing the construction of seven-membered carbocycles is of prime importance in organic synthesis given the large number of biologically relevant natural products featuring this basic unit in their (polycyclic) structure.[1] Among the different methods reported so far, the transition metal catalyzed [5+ 2] and [4+ 3] cycloadditions can certainly be considered as the most synthetically valuable.[2, 3] They indeed allow a general, convergent, and efficient access to various seven-membered rings, with the possibility to rapidly and considerably increase the structural complexity when performed in an intramolecular manner.The well-established and probably most powerful strategies to generate the 1, 4-cycloheptadienyl unit 1 rely, for instance, on either the rhodium (I)-or ruthenium (II)-catalyzed [5+ 2] cycloaddition between a vinylcyclopropane and an alkyne,[2a–d] or the rhodium (II)-catalyzed [4+ 3] cycloaddition between a diene and a vinyldiazo derivative [Eq.(1)].[2e] More recently, electrophilic platimum (II) and gold (I) species have also shown their catalytic potential to produce 1 by a [4+ 3] cycloaddition between an allene and a diene [Eq.(1)].[2f–i]