Facile access to diverse all-carbon quaternary center containing spirobicycles by exploring a tandem Castro-Stephens coupling/acyloxy shift/cyclization/semipinacol rearrangement sequence.
Facile access to diverse all-carbon quaternary center containing spirobicycles by exploring a tandem Castro-Stephens coupling/acyloxy shift/cyclization/semipinacol rearrangement sequence.
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通过探索串联卡斯特罗-斯蒂芬斯偶联/酰氧基转移/环化/半频那醇重排序列，轻松获得含有螺二环的多种全碳四元中心
DOI：
10.1039/d0sc00102c
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发表时间：
2020-03-16
期刊：
影响因子：
8.4
通讯作者：
Tu YQ
中科院分区：
文献类型：
--
作者：
Zhang Y;Zheng TL;Cheng F;Dai KL;Zhang K;Ma AJ;Zhang FM;Zhang XM;Wang SH;Tu YQ
有效地将两个或多个反应组合成一个实用的无纯化序列，对于实现结构的复杂性和多样性具有重要意义，也是开发工业上步骤经济和环境友好的新合成策略的重要途径。在这项工作中，通过实现串联的Castro-Stephens偶联/1，3-酰氧基转移/环化/半片呐醇重排序列，成功地开发了一种简便而有效的方法来构建含有一个具有合成挑战性的季碳中心的螺环[4.5]正十一烷衍生物。用这种方法合成了一系列具有苯基取代的季碳中心的多取代螺环[4.5]正庚烷和官能化的环己烷骨架，如24个例子所示，产率中等到较好。与已知的方法相比，该方法的主要优点是更好的转化效率(一次串联反应中的四次连续转化)、产物复杂性和多样性。作为对其潜在应用的支持，已经实现了关键的四环二萜骨架的快速构建。通过Castro-Stephens偶联/1，3-酰氧基转移/环化/半片呐醇重排序列合成了螺环[4.5]正十一烷衍生物。
Efficient combination of two or more reactions into a practically useful purification free sequence is of great significance for the achievement of structural complexity and diversity, and an important approach for the development of new synthetic strategies that are industrially step-economic and environmentally friendly. In this work, a facile and efficient method for the construction of highly functionalized spirocyclo[4.5]decane derivatives containing a synthetically challenging quaternary carbon center has been successfully developed through the realization of a tandem Castro–Stephens coupling/1,3-acyloxy shift/cyclization/semipinacol rearrangement sequence. Thus a series of multi-substituted spirocyclo[4.5]decane and functionalized cyclohexane skeletons with a phenyl-substituted quaternary carbon center have been constructed using this method as illustrated by 24 examples in moderate to good yields. The major advantages of this method over the known strategies are better transformation efficiency (four consecutive transformations in one tandem reaction), product complexity and diversity. As a support of its potential application, a quick construction of the key tetracyclic diterpene skeleton of waihoensene has been achieved. An efficient construction of spirocyclo[4.5]decane derivatives is developed via a Castro–Stephens coupling/1,3-acyloxy shift/cyclization/semipinacol rearrangement sequence.
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